Benzophenone derivates and its application in prepared by resistance to irradiation makrolon material
Technical field
The present invention relates to a kind of benzophenone derivates, the compound can be as the free radical stabilization of makrolon material
Agent, its xanthochromia, atomization during gamma-radiation or high-energy electron beam irradiation is prevented, the invention further relates to contain the hexichol first
The makrolon material of ketone derivatives, it has good radiation hardness, the performance of anti-xanthochromia.
Background technology
Makrolon(PC)As thermoplastic, due to its excellent performance, for example, the transparency, high tenacity, impact resistance
Property strong, heat resistance and processing dimension stability etc., the green grass or young crops of people has more and more been obtained in engineering plastics field in recent years
Look at.Polycarbonate products are not molded only or compression molding part, also film, sheet material etc..Due to excellent optics
Performance, makrolon have miscellaneous purposes in the field such as medicine equipment and consumptive material, for example, syringe, operating theater instruments, quiet
Arteries and veins transfusion, anesthesia tank, intravenous connectors and accessory, centrifugal blood bowl, blood oxygenators, blood purification, surgical instruments and
Operating room facilities etc..Makrolon has excellent mechanical strength and toughness, heat-resisting quantity and blood compatibility, in existing rank
In the high-tech Medical Devices and packaging market of section, makrolon is that one kind is especially suitable for, and the macromolecule material being accepted
Material.
, it is necessary to be sterilized when makrolon is used for medicine equipment.The ethylene oxide sterilizing used at present, due to epoxy second
Alkane itself is poisonous, residue problem be present and causes environmental pollution;And disinfection with high pressure steam can then cause makrolon in high temperature height
Aging under the conditions of wet.Irradiation sterilization is one using the microorganism caused by electromagnetic radiation on the most of materials of electromagnetic wave kill
The effective method of kind, this radiation is mostly using gamma-radiation radiation or high-power electron beam.When makrolon is exposed to sufficient dosage
Irradiation in when, resin can xanthochromia and atomization.Xanthochromia can change the color and mechanical property of makrolon material, thus can drop
The effect of low product in actual applications.Atomization can influence the transparency of makrolon, influence vision.So need to find one kind
Xanthochromia and the additive of atomization can be suppressed during makrolon irradiation sterilization.
The radiation-resistant property common practices for improving makrolon material is to add a small amount of stabilizer.For example, United States Patent (USP)
4624972 disclose a kind of esters prepared by aromatic multi-carboxy acid and alkyl substitution polyol reaction to improve makrolon material
The performance of resistance to y-radiation of material, in addition, United States Patent (USP) 4873271 discloses a kind of esters of polyalkylene oxide as stabilizer
The purpose is equally reached.Foreign countries also have some patents, such as United States Patent (USP) 5187211,4804692,4963598,
4874802nd, 5214078 be all to improve the radiation-resistant property of makrolon material by adding stabilizer.
Applicant once applied for a kind of resistance to irradiation makrolon material and its preparation method and application, the patent in 2012
In it is resistance to irradiation makrolon material be made up of makrolon, free radical stabilizer, epoxide diluent, plasticizer etc., wherein freely
Based stabilizer is 2,5 di tert butyl hydroquinone, hydroquinones dibenzyl ether, dibenzyl ketone.The patent is poly- except that can improve
Outside the yellowing problems of carbonic ester, also its mechanical property, chemical property and biological property are changed by other additives.
The content of the invention
The present invention xanthochromia, fogging problem under gamma-radiation radiation or high-power electron beam for makrolon material, there is provided
A kind of new compound --- benzophenone derivates, the compound can be as the free radical stabilizer of makrolon, Neng Goufang
Only makrolon xanthochromia, atomization during gamma-radiation or high-energy electron beam irradiation are penetrated.
Present invention also offers application of the benzophenone derivates as makrolon free radical stabilizer, and comprising
A kind of makrolon of resistance to irradiation of benzophenone derivates.Present invention also offers the simple preparation side of the resistance to irradiation makrolon
Method.
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, and G is C1-C10 alkyl or methoxyl group in formula;
In above-mentioned benzophenone derivates, the G be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group,
Nonyl, decyl, methoxyl group, preferably methyl, ethyl, propyl group, butyl, methoxyl group, most preferably methyl.
Benzophenone derivates of the present invention are reacted using friedel-craft(Friedel-Crafts)Prepare, reaction equation is as follows:
Preparation method is:In the three-necked flask equipped with thermometer and reflux condensing tube, with carbon disulfide(300ml)To be molten
Agent, the benzene of 1.0-1.5 moles of substitution is added to the chlorobenzoyl chloride and 1.0-2.0 moles of aluminum trichloride (anhydrous) of 1.0 moles of substitutions(Urge
Agent)In the mixture of formation, 40-50 DEG C is heated to, keeps boiling, back flow reaction 2-4h.Cooling, add 400ml frozen water and mix
Compound and about 120ml concentrated hydrochloric acid hydrolysis residues.Organic phase is separated, washing, dries, remove organic solvent etc., finally obtaining white
Color crystalline product.
Benzophenone derivates of the present invention can be used as free radical stabilizer, especially can be as makrolon material
Free radical stabilizer.Contain 6 substituents in benzophenone derivates of the present invention, it adds poly- carbonic acid as free radical stabilizer
Makrolon xanthochromia, atomization can be prevented in ester, mechanism is:Benzophenone derivates form stable freedom in irradiation process
Base, free radical or peroxy radical that makrolon strand is broken to form can be effectively captured, so as to cut off makrolon molecule
The photooxidation droping process of chain, reaches radiotolerant purpose.
In the molecular structure for having been reported that benzophenone ultraviolet absorbent in the prior art, it must contain at the ortho position of carbonyl
There is hydroxyl, the absorption 290-380nm ultraviolets of the benzophenone energy moderate strength containing a hydroxyl, protection is played to polymer
Effect, delays the loss of physical properties that turns yellow and reduce, available for light color and transparent article.Ultraviolet absorber and free radical of the present invention
Stabilizer is entirely different in the mechanism of action, as follows:Existing ultra-violet absorber, the hydrogen of hydroxyl and the oxygen shape of carbonyl on phenyl ring
Into intramolecular hydrogen bond, cyclic structure is formed, after ultraviolet energy is absorbed, hydrogen bond is destroyed, i.e., harmful ultraviolet is become
Heat energy discharges.And the benzophenone derivates that use of the present invention, not hydroxyl on phenyl ring(There is no the formation of intramolecular hydrogen bond
And destruction), but stable free radical is formed in irradiation process, to capture the various free radicals of makrolon strand formation,
So as to suppress the degradation process of macromolecular chain.During irradiation sterilization, the energy of gamma-rays or electron beam is much larger than ultraviolet
Line, anti-xanthochromia of the disclosed benzophenone type ultraviolet absorbent on makrolon irradiation sterilization, antifog in the prior art
Change effect is not so good as benzophenone derivates of the present invention.
A kind of makrolon of resistance to irradiation, include the composition of following parts by weight:100 parts of makrolon, free radical stabilizer
0.1-2.0 parts, the free radical stabilizer are benzophenone derivates of the present invention.
The above-mentioned makrolon of resistance to irradiation, preferably include the composition of following parts by weight:100 parts of makrolon, free radical are stable
1.0 parts of agent, the free radical stabilizer are benzophenone derivates of the present invention.
In the resistance to irradiation makrolon, the makrolon is aromatic copolycarbonate, can be the carbonic ester of homopolymerization,
It can also be the carbonic ester of copolymerization, can also be the carbonic ester of homopolymerization and copolymerization mixing.Applicable polycarbonate resin is commercially available
Product, and its structure and preparation method are all known, such as United States Patent (USP)s 3030331,3169121,3395119,372944
7th, disclosed explanation in 4255556,4260731,4369303 and 4714746.The melt flow of preferable aromatic copolycarbonate
Dynamic speed is between 10-30g/min.
The preparation method of above-mentioned resistance to irradiation makrolon material, comprises the following steps:
(1)Makrolon and free radical stabilizer are sufficiently mixed 5-10 minutes, obtain pre-composition;
(2)Control screw extruder along charge door to mouth mold direction temperature be 220-300 DEG C, die temperature 270-300
DEG C, screw speed is 40-140 revs/min, and pre-composition is added in screw extruder, stops 1-3 minute melting extrusions;
(3)After pre-composition melting extrusion, cooling, pelletizing, the makrolon material of resistance to irradiation is obtained.
The invention discloses a kind of derivative of the benzophenone with six substituents, the compound has steady well
Determine the effect of free radical, free radical stabilizer can be used as, for that can prevent makrolon in irradiation sterilization in makrolon
Middle xanthochromia and atomization, ensure the performance of makrolon.
Benzophenone derivates of the present invention are added in makrolon with 0.1-2% dosage as free radical stabilizer,
Radiotolerant makrolon can be made, the resistance to irradiation Polycarbonate Production Process is simple, easily operated implementation, in gamma-radiation
Xanthochromia, atomization can be mitigated under radiation or high energy electron beams, more conducively applied.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram spectrum of hexamethyl benzophenone of the present invention(Using deuterated acetone as solvent).
Fig. 2 is the carbon-13 nmr spectra figure of hexamethyl benzophenone of the present invention(Using deuterated acetone as solvent).
Embodiment
The present invention is further detailed below by specific embodiment, the description below is merely to explain this hair
It is bright, its content is not limited.Unless otherwise instructed, following raw materials are parts by weight.
The makrolon of following embodiments is to react obtained or bisphenol-A by interfacial polycondensation with bisphenol A disodium salt and phosgene
With diphenyl carbonate by aromatic copolycarbonate made from melt polycondensation, its melt flow rate (MFR) is in 10g/min-30g/min
Between, such makrolon has excellent physical property and impact strength, it is seen that the light transmittance more than 90% of light.
The preparation of benzophenone derivates free radical stabilizer
Embodiment 1
The free radical stabilizer that substituent is methyl is prepared, step is as follows:In three equipped with thermometer and reflux condensing tube
In mouth flask, solvent carbon disulfide 300ml is added, is stirring 2,4, the 6- trimethylbenzenes with 1.0 moles of addition under nitrogen protection
Formyl chloride, 1.3 moles of aluminum trichloride (anhydrous), 1.1 moles of 1,3,5- trimethylbenzenes are added dropwise, are heated to 45 DEG C, back flow reaction
2.5h.Cooling, add 400ml mixture of ice and water and about 120ml concentrated hydrochloric acid hydrolysis residues.Organic phase is separated, wash, dry,
Organic solvent is removed, obtains white crystalline product.
Products obtained therefrom nmr spectrum(H- is composed and C- spectrums)As depicted in figs. 1 and 2, as can be seen from the figure:Synthesis
Product is hexamethyl benzophenone.
Embodiment 2
Method according to embodiment 1 prepares the free radical stabilizer that substituent is ethyl, unlike:Raw materials used is 1,
3,5- triethylbenzenes and 2,4,6- triethylbenzene formyl chlorides, reflux time 6h.Hexaethyl benzophenone is finally given, is produced
Rate is 80%.
Embodiment 3
Method according to embodiment 1 prepares the free radical stabilizer that substituent is n-octyl, unlike:It is raw materials used to be
1,3,5- trioctylphosphine benzene and 2,4,6- trioctylphosphine chlorobenzoyl chlorides, reflux time 3h.Six octyl group benzophenone are finally given,
Yield is 60%.
Embodiment 4
Method according to embodiment 1 prepares the free radical stabilizer that substituent is methoxyl group, unlike:It is raw materials used to be
1,3,5- trimethoxy-benzene and 2,4,6- trimethoxy-benzoyl chlorides, reflux time 24h.Finally give hexa methoxy two
Benzophenone, yield 60%.
The preparation of resistance to irradiation makrolon
Embodiment 5
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 1.0 parts of the hexamethyl benzophenone of embodiment 1.
Preparation method is:Makrolon and the hexamethyl benzophenone of embodiment 1 are weighed, is sufficiently mixed 5 minutes, must premix
Thing;By pre-composition add screw extruder in melt blending, extruder along charge door to mouth mold direction temperature be 240-290 DEG C,
Die temperature is 270-290 DEG C, and screw speed is 40 revs/min, and blend obtains resistance to irradiation by die extrusion, cooling, granulation
Makrolon material.
Embodiment 6
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.3 part of the Hexaethyl benzophenone of embodiment 2.According to
The method of embodiment 5 prepares the makrolon of resistance to irradiation.
Embodiment 7
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.3 part of the six n-octyl benzophenone of embodiment 3.Press
The makrolon of resistance to irradiation is prepared according to the method for embodiment 5.
Embodiment 8
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.3 part of the hexa methoxy benzophenone of embodiment 4.Press
The makrolon of resistance to irradiation is prepared according to the method for embodiment 5.
Embodiment 9
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.3 part of the hexamethyl benzophenone of embodiment 1.According to
The method of embodiment 5 prepares the makrolon of resistance to irradiation.
Embodiment 10
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.1 part of the hexamethyl benzophenone of embodiment 1.
Preparation method is:The substituent for weighing makrolon and embodiment 1 is the benzophenone derivates of methyl, fully mixed
Close 10 minutes, obtain pre-composition;Pre-composition is added into melt blending in screw extruder, extruder is along charge door to mouth mold direction temperature
Spend for 240-290 DEG C, die temperature is 270-290 DEG C, and screw speed is 100 revs/min, blend by die extrusion, cooling,
It is granulated, obtains the makrolon material of resistance to irradiation.
Embodiment 11
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 2 parts of the hexamethyl benzophenone of embodiment 1.According to reality
The method for applying example 5 prepares the makrolon of resistance to irradiation.
Embodiment 12
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.8 part of the hexamethyl benzophenone of embodiment 1.
Preparation method is:The substituent for weighing makrolon and embodiment 1 is the benzophenone derivates of methyl, fully mixed
Close 10 minutes, obtain pre-composition;Pre-composition is added into melt blending in screw extruder, extruder is along charge door to mouth mold direction temperature
Spend for 240-290 DEG C, die temperature is 270-290 DEG C, and screw speed is 140 revs/min, blend by die extrusion, cooling,
It is granulated, obtains the makrolon material of resistance to irradiation.
Comparative example 1
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.05 part of the hexamethyl benzophenone of embodiment 1.According to
The method of embodiment 5 prepares the makrolon of resistance to irradiation.
Comparative example 2
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, ESCALOL 567(UV-9)1 part.
Method according to embodiment 5 prepares the makrolon of resistance to irradiation.
Comparative example 3
It is resistance to irradiation Polycarbonate Formulations be:100 parts of makrolon, 0.3 part of dibenzyl ketone.According to the method for embodiment 5
Prepare the makrolon of resistance to irradiation.
Examination is made according to HG/T 3862-2006 method in embodiment 5-12 and comparative example the 1-3 makrolon of resistance to irradiation
Sample.Sample is irradiated in 25Kgy Co-60 gamma-rays or in high-power electron beam to sample, placed under natural light
15 days, the yellow colour index of sample is evaluated according to national standard HG/T 3862-2006, and it is evaluated according to GB/T 2410-2008
Light transmittance, it is as a result as shown in table 1 below: