CN104311874A - Benzophenone derivative and application of benzophenone derivative in preparation of radiation resistant polycarbonate material - Google Patents
Benzophenone derivative and application of benzophenone derivative in preparation of radiation resistant polycarbonate material Download PDFInfo
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- CN104311874A CN104311874A CN201410527123.0A CN201410527123A CN104311874A CN 104311874 A CN104311874 A CN 104311874A CN 201410527123 A CN201410527123 A CN 201410527123A CN 104311874 A CN104311874 A CN 104311874A
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- polycarbonate
- resistance
- irradiation
- free radical
- benzophenone
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 107
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000005855 radiation Effects 0.000 title abstract description 11
- 150000008366 benzophenones Chemical class 0.000 title description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 34
- 239000012965 benzophenone Substances 0.000 claims abstract description 31
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003381 stabilizer Substances 0.000 claims abstract description 28
- -1 methoxyl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 33
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 abstract description 10
- 238000010894 electron beam technology Methods 0.000 abstract description 7
- 239000004425 Makrolon Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 238000009472 formulation Methods 0.000 description 11
- ISQASYCOKCUDOG-UHFFFAOYSA-N (2-methylphenyl)-(2,3,4,5,6-pentamethylphenyl)methanone Chemical compound CC1=CC=CC=C1C(=O)C1=C(C)C(C)=C(C)C(C)=C1C ISQASYCOKCUDOG-UHFFFAOYSA-N 0.000 description 10
- 230000001954 sterilising effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UDFZUGGFNFKORB-UHFFFAOYSA-N (2-ethylphenyl)-(2,3,4,5,6-pentaethylphenyl)methanone Chemical compound C(C)C1=C(C=CC=C1)C(C1=C(C(=C(C(=C1CC)CC)CC)CC)CC)=O UDFZUGGFNFKORB-UHFFFAOYSA-N 0.000 description 2
- YNALXALTXCWAEZ-UHFFFAOYSA-N (2-methoxyphenyl)-(2,3,4,5,6-pentamethoxyphenyl)methanone Chemical compound COC1=C(C=CC=C1)C(C1=C(C(=C(C(=C1OC)OC)OC)OC)OC)=O YNALXALTXCWAEZ-UHFFFAOYSA-N 0.000 description 2
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001990 intravenous administration Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BEMBJDTZNOIQDY-UHFFFAOYSA-N (2-octylphenyl)-phenylmethanone Chemical compound C(CCCCCCC)C1=C(C(=O)C2=CC=CC=C2)C=CC=C1 BEMBJDTZNOIQDY-UHFFFAOYSA-N 0.000 description 1
- WJYMPXJVHNDZHD-UHFFFAOYSA-N 1,3,5-triethylbenzene Chemical compound CCC1=CC(CC)=CC(CC)=C1 WJYMPXJVHNDZHD-UHFFFAOYSA-N 0.000 description 1
- RESHZVQZWMQUMB-UHFFFAOYSA-N 1,3-bis(phenylmethoxy)benzene Chemical compound C=1C=CC=CC=1COC(C=1)=CC=CC=1OCC1=CC=CC=C1 RESHZVQZWMQUMB-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- XVXFMSXONCJZEB-UHFFFAOYSA-N 2,4,6-trimethoxybenzoyl chloride Chemical compound COC1=CC(OC)=C(C(Cl)=O)C(OC)=C1 XVXFMSXONCJZEB-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical group CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- 206010002091 Anaesthesia Diseases 0.000 description 1
- OBORVQWFGKFKTP-UHFFFAOYSA-N C(=O)Cl.C(C)C1=CC(=CC(=C1)CC)CC Chemical compound C(=O)Cl.C(C)C1=CC(=CC(=C1)CC)CC OBORVQWFGKFKTP-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- WGMBWDBRVAKMOO-UHFFFAOYSA-L disodium;4-[2-(4-oxidophenyl)propan-2-yl]phenolate Chemical compound [Na+].[Na+].C=1C=C([O-])C=CC=1C(C)(C)C1=CC=C([O-])C=C1 WGMBWDBRVAKMOO-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
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- 230000010534 mechanism of action Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
Abstract
The invention discloses a kind of benzophenone derivates and its applications in the preparation of radiation resistance makrolon material, and structural formula is as follows, and G is the alkyl or methoxyl group of C1-C10 in formula. Benzophenone derivates of the present invention have the function of good stabilized radical, it can be used as free radical stabilizer, the derivative is added in polycarbonate as free radical stabilizer can be made radiotolerant polycarbonate, the preparation process of the radiation resistance polycarbonate is simple, easily operated implementation, xanthochromia, atomization can be mitigated under gamma-radiation radiation or high energy electron beams, more conducively applied.
Description
Technical field
The present invention relates to a kind of benzophenone derivates, this compound can as the free radical stabilizer of polycarbonate material, prevent its xanthochromia, atomization in gamma-radiation or high-energy electron beam irradiation process, the invention still further relates to the polycarbonate material containing this benzophenone derivates, it has the performance of good radiation hardness, anti-xanthochromia.
Background technology
Polycarbonate (PC) is as thermoplastics, and due to the performance of its excellence, such as, the transparency, high tenacity, shock-resistance are strong, thermotolerance and finish size stability etc., more and more obtain the favor of people in recent years in engineering plastics field.Polycarbonate products not only has injection moulding or compression molding parts, also has film, sheet material etc.Owing to having excellent optical property, polycarbonate has purposes miscellaneous in the field such as medicine equipment and consumptive material, such as, syringe, instruments, intravenous infusion, anesthesia tank, intravenous connectors and accessory, centrifugal blood bowl, blood oxygenators, blood purification, surgical instruments and operating room facilities etc.Polycarbonate has excellent physical strength and toughness, high thermal resistance and blood compatibility, and in the high-tech medical facilities and packaging market of present stage, polycarbonate is that one is very applicable, and the macromolecular material be accepted.
When polycarbonate is used for medicine equipment, need to carry out sterilizing., because oxyethane itself is poisonous, there is residue problem and cause environmental pollution in the ethylene oxide sterilizing of current employing; Disinfection with high pressure steam then can cause aging under hot and humid condition of polycarbonate.Irradiation sterilization is a kind of effective means that the hertzian wave utilizing electromagnetic radiation to produce kills the microorganism on most of material, and this radiation adopts gamma-radiation radiation or high-power electron beam mostly.When polycarbonate is exposed in the irradiation of sufficient dosage, resin can xanthochromia and atomization.Xanthochromia can change color and the mechanical property of polycarbonate material, thus can reduce product effect in actual applications.Atomization can affect the transparency of polycarbonate, affects vision.So need to find a kind of additive that can suppress xanthochromia and atomization in polycarbonate irradiation sterilization process.
The radiation-resistant property common practices improving polycarbonate material adds a small amount of stablizer.Such as, United States Patent (USP) 4624972 discloses the performance that a kind of ester class prepared by aromatic multi-carboxy acid and alkyl replacement polyol reaction improves the resistance to y-radiation of polycarbonate material, in addition, the ester class that United States Patent (USP) 4873271 discloses a kind of polyalkylene oxide reaches this object equally as stablizer.External also have some patents, and such as United States Patent (USP) 5187211,4804692,4963598,4874802,5214078 is all the radiation-resistant property improving polycarbonate material by adding stablizer.
Applicant had once applied for a kind of polycarbonate material of resistance to irradiation and its preparation method and application in 2012, in this patent, the polycarbonate material of resistance to irradiation is made up of polycarbonate, free radical stabilizer, epoxide diluent, softening agent etc., wherein free radical stabilizer is 2,5 di tert butyl hydroquinone, Resorcinol dibenzyl ether, dibenzyl ketone.This patent, except improving except the yellowing problems of polycarbonate, also changes its mechanical property, chemical property and biological property by other admixtures.
Have in the molecular structure of report benzophenone ultraviolet absorption agent in prior art; hydroxyl must be contained at the ortho position of carbonyl; the absorption 290-380nm ultraviolet of the benzophenone energy medium tenacity containing a hydroxyl; polymkeric substance is shielded; delay to turn yellow and reduce loss of physical properties, can be used for light color and transparent article.Uv-absorbing agent and free radical stabilizer of the present invention are completely different in the mechanism of action, as follows: existing UV light absorber, on phenyl ring, the hydrogen of hydroxyl and the oxygen of carbonyl form intramolecular hydrogen bond, form ring texture, when after absorption ultraviolet energy, hydrogen bond is destroyed, and namely harmful ultraviolet is become heat energy and discharges.And the benzophenone derivates that the present invention uses, not hydroxyl (not having formation and the destruction of intramolecular hydrogen bond) on phenyl ring, but in irradiation process, form stable free radical, to catch the various free radicals that polycarbonate molecular chain is formed, thus suppress the degradation process of macromolecular chain.Due in irradiation sterilization process, the energy of gamma-rays or electron beam is much larger than ultraviolet, and the absorption agent of benzophenone type ultraviolet disclosed in prior art is used in anti-xanthochromia on polycarbonate irradiation sterilization, preventing atomization effect not as benzophenone derivates of the present invention.
A kind of polycarbonate of resistance to irradiation, comprise the composition of following weight part: polycarbonate 100 parts, free radical stabilizer 0.1-2.0 part, described free radical stabilizer is benzophenone derivates of the present invention.
The above-mentioned polycarbonate of resistance to irradiation, preferably includes the composition of following weight part: polycarbonate 100 parts, free radical stabilizer 1.0 parts, and described free radical stabilizer is benzophenone derivates of the present invention.
In the described polycarbonate of resistance to irradiation, described polycarbonate is aromatic copolycarbonate, can be the carbonic ether of homopolymerization, also can be the carbonic ether of copolymerization, can also be the carbonic ether of homopolymerization and copolymerization mixing.The polycarbonate resin be suitable for has commercially available product, and its structure and preparation method are known, such as, in United States Patent (USP) 3030331,3169121,3395119,372,944 7,4255556,4260731,4369303 and 4714746 all open explanation.The melt flow rate (MFR) of preferred aromatic copolycarbonate is between 10-30g/min.
The preparation method of the above-mentioned polycarbonate material of resistance to irradiation, comprises the following steps:
(1) polycarbonate and free radical stabilizer are fully mixed 5-10 minute, obtain pre-composition;
(2) controlling screw extrusion press is 220-300 DEG C along charging opening to mouth mould direction temperature, and die temperature is 270-300 DEG C, and screw speed is 40-140 rev/min, is joined by pre-composition in screw extrusion press, stops and melt extrudes for 1-3 minute;
(3), after pre-composition melt extrudes, cooling, pelletizing, obtain the polycarbonate material of resistance to irradiation.
The invention discloses a kind of derivative with six substituent benzophenone, this compound has the effect of good stabilized radical, as free radical stabilizer, for polycarbonate xanthochromia and atomization in irradiation sterilization can be prevented in polycarbonate, the performance of polycarbonate can be ensured.
Benzophenone derivates of the present invention is as free radical stabilizer, join in polycarbonate with the consumption of 0.1-2%, radiotolerant polycarbonate can be made, this Polycarbonate Production Process of resistance to irradiation is simple, easy handling is implemented, xanthochromia, atomization can be alleviated under gamma-radiation radiation or high energy electron beams, be more conducive to application.
Summary of the invention
The present invention is directed to polycarbonate material xanthochromia, fogging problem under gamma-radiation radiation or high-power electron beam, provide a kind of new compound---benzophenone derivates, this compound can, as the free radical stabilizer of polycarbonate, can prevent polycarbonate to be emitted through xanthochromia in journey, atomization at gamma-radiation or high-energy electron beam irradiation.
Present invention also offers the application of this benzophenone derivates as polycarbonate free radical stabilizer, and comprise the one polycarbonate of resistance to irradiation of benzophenone derivates.Present invention also offers the simple method for preparing of this polycarbonate of resistance to irradiation.
The concrete technical scheme of the present invention is as follows:
A kind of benzophenone derivates, it is characterized in that: its structural formula is as follows, in formula, G is alkyl or the methoxyl group of C1-C10;
In above-mentioned benzophenone derivates, described G is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, methoxyl group, is preferably methyl, ethyl, propyl group, butyl, methoxyl group, most preferably is methyl.
Benzophenone derivates of the present invention adopts Fu-Ke reaction (Friedel-Crafts) preparation, and reaction equation is as follows:
Preparation method is: in the there-necked flask that thermometer and reflux condensing tube are housed, with dithiocarbonic anhydride (300ml) for solvent, the benzene that 1.0-1.5 mole replaces is added in the mixture that 1.0 moles of Benzoyl chlorides replaced and 1.0-2.0 mole of aluminum trichloride (anhydrous) (catalyzer) formed, be heated to 40-50 DEG C, keep boiling, back flow reaction 2-4h.Cooling, adds 400ml mixture of ice and water and about 120ml concentrated hydrochloric acid hydrolysis residue.Separate organic phase, washing, drying, removing organic solvent etc., finally obtain white crystalline product.
Benzophenone derivates of the present invention can as free radical stabilizer, especially can as the free radical stabilizer of polycarbonate material.Containing 6 substituting groups in benzophenone derivates of the present invention, it adds in polycarbonate as free radical stabilizer can prevent polycarbonate xanthochromia, atomization, mechanism is: in irradiation process, benzophenone derivates forms stable free radical, effectively can catch free radical or peroxy radical that polycarbonate molecular chain breaks to form, thus cut off the photooxidation droping process of polycarbonate molecular chain, reach radiotolerant object.
Accompanying drawing explanation
Fig. 1 is the proton nmr spectra collection of illustrative plates (taking deuterated acetone as solvent) of hexamethyl benzophenone of the present invention.
Fig. 2 is the carbon-13 nmr spectra figure (taking deuterated acetone as solvent) of hexamethyl benzophenone of the present invention.
Embodiment
Be further detailed the present invention below by specific embodiment, following explanation is only to explain the present invention, does not limit its content.If no special instructions, following raw material is weight part.
The polycarbonate of following embodiment is by the aromatic copolycarbonate that interfacial polycondensation reacts obtained or dihydroxyphenyl propane is obtained by melt phase polycondensation with diphenyl carbonate with bisphenol A disodium salt and phosgene, its melt flow rate (MFR) is between 10g/min-30g/min, such polycarbonate has excellent physicals and shock strength, the transmittance more than 90% of visible ray.
the preparation of benzophenone derivates free radical stabilizer
embodiment 1
Prepare the free radical stabilizer that substituting group is methyl; step is as follows: in the there-necked flask that thermometer and reflux condensing tube are housed; add solvent carbon disulfide 300ml, under stirring and nitrogen protection, add 1.0 moles 2,4; 6-tri-methyl chloride, the aluminum trichloride (anhydrous) of 1.3 moles; drip the 1，3，5-trimethyl-benzene of 1.1 moles; be heated to 45 DEG C, back flow reaction 2.5h.Cooling, adds 400ml mixture of ice and water and about 120ml concentrated hydrochloric acid hydrolysis residue.Separate organic phase, washing, dry, removing organic solvent, obtain white crystalline product.
Products obtained therefrom nmr spectrum (H-spectrum and C-spectrum) as depicted in figs. 1 and 2, can from figure
go out:the product of synthesis is hexamethyl benzophenone.
embodiment 2
The free radical stabilizer that substituting group is ethyl is prepared according to the method for embodiment 1, unlike: raw materials used is 1,3,5-triethylbenzene and 2,4,6-triethylbenzene formyl chloride, and reflux time is 6h.Finally obtain Hexaethyl benzophenone, productive rate is 80%.
embodiment 3
The free radical stabilizer that substituting group is n-octyl is prepared according to the method for embodiment 1, unlike: raw materials used is 1,3,5-trioctylphosphine benzene and 2,4,6-trioctylphosphine Benzoyl chloride, and reflux time is 3h.Finally obtain six octyl group benzophenone, productive rate is 60%.
embodiment 4
The free radical stabilizer that substituting group is methoxyl group is prepared according to the method for embodiment 1, unlike: raw materials used is 1,3,5-trimethoxy-benzene and 2,4,6-trimethoxy-benzoyl chloride, and reflux time is 24h.Finally obtain hexa methoxy benzophenone, productive rate is 60%.
the preparation of the polycarbonate of resistance to irradiation
embodiment 5
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the hexamethyl benzophenone of embodiment 1 1.0 parts.
Preparation method is: the hexamethyl benzophenone taking polycarbonate and embodiment 1, and fully mixing 5 minutes, obtains pre-composition; Pre-composition is added melt blending in screw extrusion press, forcing machine is 240-290 DEG C along charging opening to mouth mould direction temperature, and die temperature is 270-290 DEG C, and screw speed is 40 revs/min, blend, through die extrusion, cooling, granulation, obtains the polycarbonate material of resistance to irradiation.
embodiment 6
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the Hexaethyl benzophenone of embodiment 2 0.3 part.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
embodiment 7
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the six n-octyl benzophenone 0.3 part of embodiment 3.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
embodiment 8
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the hexa methoxy benzophenone of embodiment 4 0.3 part.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
embodiment 9
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the hexamethyl benzophenone of embodiment 1 0.3 part.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
embodiment 10
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the hexamethyl benzophenone of embodiment 1 0.1 part.
Preparation method is: the substituting group taking polycarbonate and embodiment 1 is the benzophenone derivates of methyl, and fully mixing 10 minutes, obtains pre-composition; Pre-composition is added melt blending in screw extrusion press, forcing machine is 240-290 DEG C along charging opening to mouth mould direction temperature, and die temperature is 270-290 DEG C, and screw speed is 100 revs/min, blend, through die extrusion, cooling, granulation, obtains the polycarbonate material of resistance to irradiation.
embodiment 11
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the hexamethyl benzophenone of embodiment 12 parts.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
embodiment 12
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the hexamethyl benzophenone of embodiment 1 0.8 part.
Preparation method is: the substituting group taking polycarbonate and embodiment 1 is the benzophenone derivates of methyl, and fully mixing 10 minutes, obtains pre-composition; Pre-composition is added melt blending in screw extrusion press, forcing machine is 240-290 DEG C along charging opening to mouth mould direction temperature, and die temperature is 270-290 DEG C, and screw speed is 140 revs/min, blend, through die extrusion, cooling, granulation, obtains the polycarbonate material of resistance to irradiation.
comparative example 1
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, the hexamethyl benzophenone of embodiment 1 0.05 part.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
comparative example 2
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, ESCALOL 567 (UV-9) 1 part.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
comparative example 3
The Polycarbonate Formulations of resistance to irradiation is: polycarbonate 100 parts, dibenzyl ketone 0.3 part.The polycarbonate of resistance to irradiation is prepared according to the method for embodiment 5.
The polycarbonate of resistance to irradiation of embodiment 5-12 and comparative example 1-3 is made sample according to the method for HG/T 3862-2006.Sample is exposed in the Co-60 gamma-rays of 25Kgy or high-energy electron is intrafascicular carries out irradiation to sample, place 15 days under natural light, according to the yellowness index of national standard HG/T 3862-2006 assess sample, and evaluate its transmittance according to GB/T 2410-2008, result is as shown in table 1 below:
Claims (9)
1. a benzophenone derivates, is characterized in that: its structural formula is as follows, and in formula, G is alkyl or the methoxyl group of C1-C10;
。
2. benzophenone derivates according to claim 1, is characterized in that: described G is methyl.
3. the benzophenone derivates described in a claim 1 or 2 is as the application of free radical stabilizer.
4. the polycarbonate of resistance to irradiation, is characterized in that the composition comprising following weight part: polycarbonate 100 parts, free radical stabilizer 0.1-2.0 part, and described free radical stabilizer is the benzophenone derivates described in claim 1 or 2.
5. the polycarbonate of resistance to irradiation according to claim 4, is characterized in that the composition comprising following weight part: polycarbonate 100 parts, free radical stabilizer 1.0 parts.
6. the polycarbonate of resistance to irradiation according to claim 4 or 5, is characterized in that: described polycarbonate is aromatic copolycarbonate.
7. the polycarbonate of resistance to irradiation according to claim 6, is characterized in that: described polycarbonate is the carbonic ether of the carbonic ether of homopolymerization, the carbonic ether of copolymerization or homopolymerization and copolymerization mixing.
8. the polycarbonate of resistance to irradiation according to claim 4,6 or 7, is characterized in that: the melt flow rate (MFR) of described polycarbonate is 10-30g/min.
9. a preparation method for the polycarbonate material of resistance to irradiation according to claim 4, is characterized in that comprising the following steps:
(1) polycarbonate and free radical stabilizer are fully mixed 5-10 minute, obtain pre-composition;
(2) controlling screw extrusion press is 220-300 DEG C along charging opening to mouth mould direction temperature, and die temperature is 270-300 DEG C, and screw speed is 40-140 rev/min, is joined by pre-composition in screw extrusion press, stops and melt extrudes for 1-3 minute;
(3), after pre-composition melt extrudes, cooling, pelletizing, obtain the polycarbonate material of resistance to irradiation.
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| CN1775828A (en) * | 2005-11-21 | 2006-05-24 | 中国科学院长春应用化学研究所 | Method for preparing crosslinked aliphatic series polycarbonate |
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| CN1775828A (en) * | 2005-11-21 | 2006-05-24 | 中国科学院长春应用化学研究所 | Method for preparing crosslinked aliphatic series polycarbonate |
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