CN105418831B - The synthetic method of the luminous polypropylene acrylic materials of the polyhedral oligomeric silsesquioxane rare earth compounding of function containing esters of acrylic acid - Google Patents
The synthetic method of the luminous polypropylene acrylic materials of the polyhedral oligomeric silsesquioxane rare earth compounding of function containing esters of acrylic acid Download PDFInfo
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- CN105418831B CN105418831B CN201510969705.9A CN201510969705A CN105418831B CN 105418831 B CN105418831 B CN 105418831B CN 201510969705 A CN201510969705 A CN 201510969705A CN 105418831 B CN105418831 B CN 105418831B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The present invention relates to a kind of synthetic method of the luminous polypropylene acrylic materials of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding, make esters of acrylic acid function polyhedral oligomeric silsesquioxane that coordination occur with rare earth compound first with Coordinative Chemistry principle, then esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding is distributed in acrylic monomer again and polymerisation in bulk in situ occurs, finally give with good light permeability, the luminous polypropylene acrylic materials of heat endurance and the function containing esters of acrylic acid of fluorescence property polyhedral oligomeric silsesquioxane rare earth compounding.Synthesis step of the present invention is simple, mild condition, and without any additive, condition is easily controllable, and whole synthesis device is easy to build, and has very big novelty, is easy to industrialized production luminous polypropylene acrylic materials.
Description
Technical field
The present invention relates to a kind of the luminous of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The synthetic method of polyacrylic materials, belong to rare earth high polymer composite functional material field.
Background technology
Rare earth luminescent material such as is widely used in illuminating, show and detect at the field, forms very big industrial production and disappears
Take market scale, and just expanded to other emerging technologies (such as solid-state dye laser, false proof) field rapidly.Due to containing dilute
The high-molecular luminous material of native complex has the luminescent properties of rare earth ion concurrently and the characteristics of stabilizing polymer is good, easy processing,
Extensive concern is caused.Its research method is basically divided into two kinds:(1) rare earth small molecule is directly mixed to get doping with macromolecule
The Luminescence of Rare Earth Polymer Complex of type；(2) rare earth compounding of polymerisation can be occurred by first being synthesized by the method for chemical bonding
Monomer, then it polymerize to obtain rare earth high polymer copolymer fluorescent material, or rare earth ion and macromolecule with other organic monomers
Ligand groups such as carboxyl, sulfonic group react obtained Luminescence of Rare Earth Polymer Complex on chain.The most frequently used method is by rare earth
Compound is distributed in monomer or polymer as dopant, is made with rare earth high polymer fluorescent polymer existing for doping way,
Its preparation technology is simpler, and production cost is relatively low, is widely used in many aspects.But because rare earth compounding is in polymeric matrix
It is middle the shortcomings of dispersiveness is bad, is easily separated with matrix to be present, thus cause doping type rare earth high polymer material stability
Difference, generation concentration is quenched between fluorescence molecule, and fluorescence intensity reduces, and fluorescence lifetime declines.Chemical bond mould assembly rare earth high polymer can
Overcome the rare earth compounding that doping type rare earth high polymer is often presented and resin affinity poor, material transparent and poor mechanical property etc.
Shortcoming, the rare earth high polymer functional material for the wide content of rare earth of acquisition, high transmission rate provide an effective way, caused
The great interest of people.
In rare earth compounding, rare earth organic complex is easy to produce solvation effect because itself photo and thermal stability is poor
Cause fluorescent quenching, and limit its use range.New hybrid inorganic-organic rare earth compounding can substantially improve this
Situation.In recent years, polyhedral oligomeric silsesquioxane (abbreviation POSS) is because of its excellent heat endurance and easily designed functionalization
The characteristics of caused the great interest of people.It is coordinated to form POSS base rare earth compoundings using rare earth compound and POSS, then
It is copolymerized with polymer monomer, wide content of rare earth, the rare earth high polymer composite functional material of high transmission rate can be prepared.
Chinese patent document CN104193860A (application numbers：201410403041.5) disclose a kind of multiaspect containing rare earth
The synthetic method of body oligomeric silsesquioxane based high molecular composite luminescent material, first will will be through organic using Coordinative Chemistry principle
The method and the first ligand rare earth ion that the polyhedral oligomeric silsesquioxane of ligand-modified cage structure passes through collosol and gel
Coordination, being then re-introduced into can be coordinated with the polymethyl methacrylate of rare-earth ion coordination as Ligands, final
Polyhedral oligomeric silsesquioxane base to the cage structure containing rare earth with good fluorescence property and heat endurance is high
Molecule composite luminescent material.But on the one hand the above method needs first with organic ligands such as acetylacetone,2,4-pentanedione or salicylic acids to be matched somebody with somebody
Position, preparation process are complicated；On the other hand, the polyhedral oligomeric silsesquioxane of the cage structure used is the monoamine of cage structure
The sulfydryl polyhedral oligomeric silsesquioxane of polyhedral oligomeric silsesquioxane or cage structure, it is impossible to direct with rare earth element
Coordination, nor copolyreaction can be carried out.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of polyhedral oligomeric silsesquioxane of function containing esters of acrylic acid
The synthetic method of the luminous polypropylene acrylic materials of alkane rare earth compounding.Make esters of acrylic acid work(first with Coordinative Chemistry principle
With rare earth compound coordination occurs for energy polyhedral oligomeric silsesquioxane, then again by esters of acrylic acid function Quito face
Body oligomeric silsesquioxane rare earth compounding, which is distributed in acrylic monomer, occurs polymerisation in bulk in situ, finally gives with good
The polyhedral oligomeric silsesquioxane rare earth compounding of function containing esters of acrylic acid of good translucency, heat endurance and fluorescence property
Luminous polypropylene acrylic materials.
Technical scheme is as follows：
A kind of luminous polypropylene acids of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The synthetic method of material, including step are as follows：
(1) rare earth nitrades are dissolved into organic solvent, add esters of acrylic acid function polyhedral oligomeric sesquialter silicon
Oxygen alkane, stirs 1-10h at room temperature, by the reaction solution rotary evaporation of gained, obtains esters of acrylic acid function polyhedral oligomeric sesquialter
Siloxanes rare earth compounding；
(2) it is the esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding obtained by step (1) is molten
In organic solvent, it is then added in acrylic monomer, 5-10min is stirred at room temperature, removal of solvent under reduced pressure, adds initiator,
Bulk polymerization in situ is carried out, is produced.
, according to the invention it is preferred to, rare earth nitrades described in step (1) are terbium nitrate, europium nitrate, neodymium nitrate or
Dysprosium nitrate；
Preferably, described organic solvent is tetrahydrofuran, chloroform, acetone, acetonitrile or ethanol, and consumption of organic solvent is pressed
Esters of acrylic acid function polyhedral oligomeric silsesquioxane：Organic solvent is 1mol:10-20mL ratio；
Preferably, the mol ratio of esters of acrylic acid function polyhedral oligomeric silsesquioxane and rare earth nitrades is 1:
0.1-2.5。
, according to the invention it is preferred to, the esters of acrylic acid function polyhedral oligomeric silsesquioxane described in step (1)
With following structure：
(SiO1.5)n(CH2CH2CH2OCOCHCH2)n
Or
(SiO1.5)n(CH2CH2CH2OCOC(CH3)CH2)n, n=8,10 or 12；
Preferably, described esters of acrylic acid function polyhedral oligomeric silsesquioxane is methyl acrylate polyhedral
Oligomeric silsesquioxane or methyl methacrylate polyhedral oligomeric silsesquioxane；It is further preferred that acrylic acid first
Ester group polyhedral oligomeric silsesquioxane is eight methyl acrylate base oligomeric silsesquioxanes, the ten oligomeric sesquialters of methyl acrylate base
Siloxanes or/and ten diacrylate carbomethoxy oligomeric silsesquioxanes, methyl methacrylate polyhedral oligomeric silsesquioxane
Alkane is prestox methyl acrylate base oligomeric silsesquioxane, decamethyl methyl acrylate base oligomeric silsesquioxane or/and ten
Methyl methacrylate base oligomeric silsesquioxane.
According to the present invention, esters of acrylic acid function polyhedral oligomeric silsesquioxane is commercially available, also can be by prior art
It is prepared, reference can be made to Li, L.；Liang,R.；Li,Y.；Liu,H.；Feng,S.,Hybrid thiol-ene network
nanocomposites based on multi(meth)acrylate POSS.Journal of colloid and
interface science 2013,406,30-6.
Preferably it is prepared as follows obtaining：
Chloropropyl polyhedral oligomeric silsesquioxane is dissolved into organic solvent, then adds potassium acrylate or methyl
Potassium acrylate, then add KI, control temperature for 100 DEG C reaction 12h, by the reacting liquid filtering of gained, revolving, washing,
Rotate again, obtained yellow oil is methyl acrylate polyhedral oligomeric silsesquioxane or methyl methacrylate
Ester group polyhedral oligomeric silsesquioxane.
, according to the invention it is preferred to, organic solvent described in step (2) is tetrahydrofuran, chloroform, acetone, acetonitrile or
Ethanol, consumption of organic solvent press esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding：Organic solvent is
1mol:1-10mL ratio；
Preferably, described acrylic monomer is more than one or both of acrylic compounds and its ester mixed
Close；
Preferably, described esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding and acrylic compounds
The mass percent of monomer is 1-15%:100%；
Preferably, described initiator is azodiisobutyronitrile or benzoyl peroxide and all can trigger free radical
The mass percent of the initiator of polymerization, initiator and acrylic monomer is 2%：100%.
, according to the invention it is preferred to, step (2) situ bulk polymerization process is：2h, 70 DEG C of guarantors are kept in 60 DEG C
Hold 2h, 90 DEG C of holdings 36h, 100 DEG C of holding 1h.
Beneficial effects of the present invention
1st, the present invention by copolyreaction by esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding
Be incorporated into polyacrylic materials matrix, overcome rare earth compounding in the polymer matrix it is dispersed it is bad, it is easy be separated,
The shortcomings that translucency difference, while the shortcomings that overcome poor traditional rare earth organic coordination compound photo and thermal stability, easy fluorescent quenching.Finally
The stable polyhedral oligomeric of function containing esters of acrylic acid of wide content of rare earth, high light transmittance, high heat stability, fluorescence property is obtained
The luminous polypropylene acrylic materials of silsesquioxane rare earth compounding.
2nd, the preparation process of complex of the present invention is simple and convenient is easy to get.
3rd, the esters of acrylic acid function polyhedral oligomeric silsesquioxane synthetic method in the present invention is simple, while propylene
Coordination both can directly occur with rare earth element for esters of gallic acid function polyhedral oligomeric silsesquioxane, again can be with propylene
Acids class monomer is copolymerized, and is advantageous to esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding
In the polymer matrix dispersed.The luminous polypropylene acrylic materials thermostabilization of the high light transmittance finally given is also more preferable.
4th, synthesis step of the present invention is simple, mild condition, and without any additive, condition is easily controllable, and synthesis device is easy
In building, product is easily handled, and is easy to industrial applications.
Brief description of the drawings
Fig. 1 is the methyl methacrylate polyhedral oligomeric silsesquioxane rare earth terbium obtained by step (1) in embodiment 1
The silsesquioxane rare-earth terbium complex of polyhedral oligomeric containing methyl methacrylate obtained by complex and step (2) it is luminous
The infrared spectrogram of polymethyl methacrylate；
Fig. 2 is that the silsesquioxane rare earth of polyhedral oligomeric containing the methyl methacrylate terbium of gained in embodiment 1 coordinates
The luminous polymethyl methacrylate of thing and the thermogravimetric curve of pure polymethyl methacrylate；
Fig. 3 is the methyl methacrylate polyhedral oligomeric silsesquioxane rare earth terbium obtained by step (1) in embodiment 1
The luminous of the rare-earth terbium complex of polyhedral oligomeric silsesquioxane containing methyl methacrylate obtained by complex and step (2) gathers
The fluorescent exciting spectrogram and launching light spectrogram of methyl methacrylate.
Fig. 4 is the rare-earth terbium complex of polyhedral oligomeric silsesquioxane containing methyl methacrylate of gained in embodiment 1
Luminous polymethyl methacrylate transmission electron microscope figure of the ultra-thin section under different multiplying.
Embodiment
Below by specific embodiment and with reference to accompanying drawing, the present invention is further described, but protection scope of the present invention is not
It is limited to these embodiments.
Can be respectively with infrared using the homogeneity of the structure of products therefrom of the present invention, heat endurance, photism and material
Spectrum (FTIR), thermogravimetric analysis (TGA), fluorescence spectrum (PL) and transmission electron microscope (TEM) etc. are characterized.
Raw material used in various embodiments of the present invention, synthesize for conventional raw material purchased in market or according to bibliography method
Arrive.
Wherein, esters of acrylic acid function polyhedral oligomeric silsesquioxane has following structure：
(SiO1.5)n(CH2CH2CH2OCOCHCH2)n
Or
(SiO1.5)n(CH2CH2CH2OCOC(CH3)CH2)n, n=8,10 or 12；
Referring to Li, L.；Liang,R.；Li,Y.；Liu,H.；Feng,S.,Hybrid thiol-ene network
nanocomposites based on multi(meth)acrylate POSS.Journal of colloid and
Interface science 2013,406,30-6. are made.
Embodiment 1
A kind of luminous polypropylene acids of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The synthetic method of material, including step are as follows：
(1) preparation of esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding
0.388g terbium nitrates are put into measuring cup, add 20mL tetrahydrofurans, agitating solution to terbium nitrate is completely dissolved
Afterwards, 0.612g esters of acrylic acid function polyhedral oligomeric silsesquioxanes are weighed, 1-10h are stirred at room temperature, by the anti-of gained
Liquid rotary evaporation is answered, obtained compound is that esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth terbium coordinates
Thing.
Described esters of acrylic acid function polyhedral oligomeric silsesquioxane is oligomeric times of prestox methyl acrylate base
Half siloxanes, decamethyl methyl acrylate base oligomeric silsesquioxane and ten methyl methacrylate base oligomeric silsesquioxanes
Mixture.
(2) the luminous polypropylene acids material of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The preparation of material
Esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth terbium obtained by 0.05g steps (1) is coordinated
Thing is dissolved in 1mL tetrahydrofurans, is then added into 1.00g methyl methacrylate monomers, 5-10min is stirred at room temperature,
Removal of solvent under reduced pressure, 0.02g benzoyl peroxides are added, carry out bulk polymerization in situ.Polymerization process is in air blast
60 DEG C of holdings 2h, 70 DEG C of holdings 2h, 90 DEG C of holdings 36h, 100 DEG C of holding 1h in drying box.Finally give and transparent contained propylene
The luminous polymethyl methacrylate of esters of gallic acid function polyhedral oligomeric silsesquioxane rare-earth terbium complex.
Using Bruker TENSOR-27 types infrared spectrometers to methyl methacrylate Quito obtained by above-mentioned steps (1)
The sesquialter of polyhedral oligomeric containing methyl methacrylate obtained by face body oligomeric silsesquioxane rare-earth terbium complex and step (2)
The structure of the luminous polymethyl methacrylate of siloxanes rare-earth terbium complex is characterized, with methyl methacrylate Quito face
Body oligomeric silsesquioxane is reference, and the infared spectrum of gained is as shown in Figure 1.A curves are methyl methacrylate Quito in Fig. 1
The infrared spectrum of face body oligomeric silsesquioxane, b curves are methyl methacrylate polyhedral oligomeric silsesquioxane rare earth
The infrared spectrum of terbium coordination compound, c curves are the silsesquioxane rare-earth terbium complex of polyhedral oligomeric containing methyl methacrylate
Luminous polymethyl methacrylate infrared spectrum.Terbium nitrate and methyl methacrylate are can be seen that from the b curves in Fig. 1
The characteristic peak of polyhedral oligomeric silsesquioxane can show, and be indicated above methyl methacrylate polyhedral oligomeric sesquialter
Siloxanes is successfully coordinated with terbium nitrate.
Using Mettler-Toledo TGA/DSC thermal gravimetric analyzers (40-800 DEG C, 10 DEG C/min, N2) to above-mentioned step
Suddenly the luminous polymethyl of the silsesquioxane rare-earth terbium complex of polyhedral oligomeric containing methyl methacrylate obtained by (2)
The heat endurance of sour methyl esters is characterized, using pure polymethyl methacrylate as control, thermogravimetric curve such as Fig. 2 of gained
It is shown.A curves are the thermogravimetric curve of pure polymethyl methacrylate in Fig. 2, and b curves are the face of Quito containing methyl methacrylate
The thermogravimetric curve of the luminous polymethyl methacrylate of body oligomeric silsesquioxane rare-earth terbium complex.As can be seen from Figure 2
The luminous polymethyl methacrylate of the silsesquioxane rare-earth terbium complex of polyhedral oligomeric containing methyl methacrylate is than pure
The temperature of initial decomposition of polymethyl methacrylate is high, and decomposition curve also more slowly, has been indicated above containing methyl methacrylate
The luminous polymethyl methacrylate of polyhedral oligomeric silsesquioxane rare-earth terbium complex is than pure polymethyl methacrylate
Heat endurance it is good.
Methyl methacrylate using HITACHI F-7000 types XRFs to the gained obtained by above-mentioned steps (1)
Polyhedral containing methyl methacrylate obtained by ester group polyhedral oligomeric silsesquioxane rare-earth terbium complex and step (2) is low
The luminous polymethyl methacrylate of polysilsesquioxane rare-earth terbium complex is measured.Transmitting spectrogram such as Fig. 3 institutes of gained
Show.A curves are the fluorescence spectrum of methyl methacrylate polyhedral oligomeric silsesquioxane rare-earth terbium complex in Fig. 3, and b is bent
Line is the luminous polymethyl methacrylate of the silsesquioxane rare-earth terbium complex of polyhedral oligomeric containing methyl methacrylate
Fluorescence spectrum.As can be seen from Figure 3 the methyl methacrylate polyhedral oligomeric silsesquioxane obtained by step (1) is dilute
The silsesquioxane rare-earth terbium complex of polyhedral oligomeric containing methyl methacrylate obtained by native terbium coordination compound and step (2)
There is the characteristic emission peak of terbium ion in luminous polymethyl methacrylate.
Using JEM-1011 types transmission electron microscope to the face of Quito containing methyl methacrylate obtained by above-mentioned steps (2)
The luminous polymethyl methacrylate of body oligomeric silsesquioxane rare-earth terbium complex is measured.It is different times magnifications in Fig. 4
The luminous polymethyl methacrylate of the silsesquioxane of polyhedral oligomeric containing methyl methacrylate rare-earth terbium complex under several
Ultra-thin section transmission electron microscope figure.Methyl methacrylate polyhedral oligomeric silsesquioxane as can be seen from Figure 4
Rare-earth terbium complex is uniformly dispersed in polymethyl methacrylate base matter, and its particle size is about 15-20nm, illustrates methyl
Methyl acrylate polyhedral oligomeric silsesquioxane rare-earth terbium complex has reached in polymethyl methacrylate base matter to be received
Meter level is other scattered, i.e., both can be copolymerized.
Embodiment 2
A kind of luminous polypropylene acids of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The synthetic method of material, including step are as follows：
(1) preparation of esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding
0.768g terbium nitrates are put into measuring cup, add 20mL tetrahydrofurans, agitating solution to terbium nitrate is completely dissolved
Afterwards, 1.226g prestox methyl acrylate bases oligomeric silsesquioxane, decamethyl methyl acrylate base oligomeric silsesquioxane are added
The mixture of alkane and ten methyl methacrylate base oligomeric silsesquioxanes, stirs 1-10h at room temperature, by the reaction solution of gained
Rotary evaporation, obtained compound are esters of acrylic acid function polyhedral oligomeric silsesquioxane rare-earth terbium complex.
(2) the luminous polypropylene acids material of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The preparation of material
Esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth terbium obtained by 0.10g steps (1) is coordinated
Thing is dissolved in 1mL tetrahydrofurans, is then added into 1.00g methyl methacrylate monomers, 5-10min is stirred at room temperature,
Removal of solvent under reduced pressure, 0.02g benzoyl peroxides are added, carry out bulk polymerization in situ.Polymerization process is in air blast
60 DEG C of holdings 2h, 70 DEG C of holdings 2h, 90 DEG C of holdings 36h, 100 DEG C of holding 1h in drying box.Finally give and transparent contained propylene
The luminous polymethyl methacrylate of esters of gallic acid function polyhedral oligomeric silsesquioxane rare-earth terbium complex.
Using Bruker TENSOR-27 types infrared absorption spectrometers to the esters of acrylic acid function obtained by above-mentioned steps (1)
The polyhedral oligomeric of function containing esters of acrylic acid obtained by polyhedral oligomeric silsesquioxane rare-earth terbium complex and step (2)
The structure of the luminous polymethyl methacrylate of silsesquioxane rare-earth terbium complex is characterized, as a result terbium nitrate and acrylic acid
The characteristic peak of esters function polyhedral oligomeric silsesquioxane can show, and be indicated above esters of acrylic acid function polyhedral
Oligomeric silsesquioxane is successfully coordinated with terbium nitrate.
Using Mettler-Toledo TGA/DSC thermal gravimetric analyzers (40-800 DEG C, 10 DEG C/min, N2) to above-mentioned step
Suddenly the luminous polymethyl of the polyhedral oligomeric silsesquioxane rare-earth terbium complex of function containing esters of acrylic acid obtained by (2)
The heat endurance of sour methyl esters is characterized, using pure polymethyl methacrylate as control, the results showed that containing esters of acrylic acid
The luminous polymethyl methacrylate of function polyhedral oligomeric silsesquioxane rare-earth terbium complex is than pure polymethylacrylic acid
The temperature of initial decomposition of methyl esters is high, and decomposition curve also more slowly, has been indicated above the polyhedral oligomeric of function containing esters of acrylic acid
The luminous polymethyl methacrylate of silsesquioxane rare-earth terbium complex is better than the heat endurance of pure polymethyl methacrylate.
Esters of acrylic acid work(using HITACHI F-7000 types XRFs to the gained obtained by above-mentioned steps (1)
The polyhedral of function containing esters of acrylic acid obtained by energy polyhedral oligomeric silsesquioxane rare-earth terbium complex and step (2) is low
The luminous polymethyl methacrylate of polysilsesquioxane rare-earth terbium complex is measured.As a result show obtained by step (1)
Work(containing esters of acrylic acid obtained by esters of acrylic acid function polyhedral oligomeric silsesquioxane rare-earth terbium complex and step (2)
There is the spy of terbium ion in the luminous polymethyl methacrylate of energy polyhedral oligomeric silsesquioxane rare-earth terbium complex
Levy emission peak.
Embodiment 3
A kind of luminous polypropylene acids of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The synthetic method of material, including step are as follows：
(1) preparation of esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding
1.162g terbium nitrates are put into measuring cup, add 20mL tetrahydrofurans, agitating solution to terbium nitrate is completely dissolved
Afterwards, 1.838g prestox methyl acrylate bases oligomeric silsesquioxane, decamethyl methyl acrylate base oligomeric silsesquioxane are added
The mixture of alkane and ten methyl methacrylate base oligomeric silsesquioxanes, stirs 1-10h at room temperature, by the reaction solution of gained
Rotary evaporation, obtained compound are esters of acrylic acid function polyhedral oligomeric silsesquioxane rare-earth terbium complex.
(2) the luminous polypropylene acids material of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The preparation of material
Esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth terbium obtained by 0.15g steps (1) is coordinated
Thing is dissolved in 1mL tetrahydrofurans, is then added into 1.00g methyl methacrylate monomers, 5-10min is stirred at room temperature,
Removal of solvent under reduced pressure, 0.02g benzoyl peroxides are added, carry out bulk polymerization in situ.Polymerization process is in air blast
60 DEG C of holdings 2h, 70 DEG C of holdings 2h, 90 DEG C of holdings 36h, 100 DEG C of holding 1h in drying box.Finally give and transparent contained propylene
The luminous polymethyl methacrylate of esters of gallic acid function polyhedral oligomeric silsesquioxane rare-earth terbium complex.
Using Bruker TENSOR-27 types infrared absorption spectrometers to the esters of acrylic acid function obtained by above-mentioned steps (1)
The polyhedral oligomeric of function containing esters of acrylic acid obtained by polyhedral oligomeric silsesquioxane rare-earth terbium complex and step (2)
The structure of the luminous polymethyl methacrylate of silsesquioxane rare-earth terbium complex is characterized, as a result terbium nitrate and acrylic acid
The characteristic peak of esters function polyhedral oligomeric silsesquioxane can show, and be indicated above esters of acrylic acid function polyhedral
Oligomeric silsesquioxane is successfully coordinated with terbium nitrate.
Using Mettler-Toledo TGA/DSC thermal gravimetric analyzers (40-800 DEG C, 10 DEG C/min, N2) to above-mentioned step
Suddenly the luminous polymethyl of the polyhedral oligomeric silsesquioxane rare-earth terbium complex of function containing esters of acrylic acid obtained by (2)
The heat endurance of sour methyl esters is characterized, using pure polymethyl methacrylate as control, the results showed that containing esters of acrylic acid
The luminous polymethyl methacrylate of function polyhedral oligomeric silsesquioxane rare-earth terbium complex is than pure polymethylacrylic acid
The temperature of initial decomposition of methyl esters is high, and decomposition curve also more slowly, has been indicated above the polyhedral oligomeric of function containing esters of acrylic acid
The luminous polymethyl methacrylate of silsesquioxane rare-earth terbium complex is better than the heat endurance of pure polymethyl methacrylate.
Esters of acrylic acid work(using HITACHI F-7000 types XRFs to the gained obtained by above-mentioned steps (1)
The polyhedral of function containing esters of acrylic acid obtained by energy polyhedral oligomeric silsesquioxane rare-earth terbium complex and step (2) is low
The luminous polymethyl methacrylate of polysilsesquioxane rare-earth terbium complex is measured.As a result show obtained by step (1)
Work(containing esters of acrylic acid obtained by esters of acrylic acid function polyhedral oligomeric silsesquioxane rare-earth terbium complex and step (2)
There is the spy of terbium ion in the luminous polymethyl methacrylate of energy polyhedral oligomeric silsesquioxane rare-earth terbium complex
Levy emission peak.
Embodiment 4
A kind of luminous polypropylene acids of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The synthetic method of material, including step are as follows：
(1) preparation of esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding
0.381g europium nitrates are put into measuring cup, add 20mL tetrahydrofurans, agitating solution to europium nitrate is completely dissolved
Afterwards, 0.612g prestox methyl acrylate bases oligomeric silsesquioxane, decamethyl methyl acrylate base oligomeric silsesquioxane are weighed
The mixture of alkane and ten methyl methacrylate base oligomeric silsesquioxanes, stirs 1-10h at room temperature, by the reaction solution of gained
Rotary evaporation, obtained compound are esters of acrylic acid function polyhedral oligomeric silsesquioxane Rare Earth Europium Complex.
(2) the luminous polypropylene acids material of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The preparation of material
Esters of acrylic acid function polyhedral oligomeric silsesquioxane rare-earth europium obtained by 0.05g steps (1) is coordinated
Thing is dissolved in 1mL tetrahydrofurans, is then added into 1.00g methacrylate monomers, and 5-10min is stirred at room temperature, decompression
Solvent is removed, 0.02g benzoyl peroxides is added, carries out bulk polymerization in situ.Polymerization process is in forced air drying
60 DEG C of holdings 2h, 70 DEG C of holdings 2h, 90 DEG C of holdings 36h, 100 DEG C of holding 1h in case.Finally give and transparent contained acrylate
The luminous polypropylene acid methyl esters of class function polyhedral oligomeric silsesquioxane Rare Earth Europium Complex.
Using Bruker TENSOR-27 types infrared absorption spectrometers to the esters of acrylic acid function obtained by above-mentioned steps (1)
The polyhedral oligomeric of function containing esters of acrylic acid obtained by polyhedral oligomeric silsesquioxane Rare Earth Europium Complex and step (2)
The structure of the luminous polypropylene acid methyl esters of silsesquioxane Rare Earth Europium Complex is characterized, as a result europium nitrate and esters of acrylic acid
The characteristic peak of function polyhedral oligomeric silsesquioxane can show, and be indicated above esters of acrylic acid function polyhedral oligomeric
Silsesquioxane is successfully coordinated with europium nitrate.
Using Mettler-Toledo TGA/DSC thermal gravimetric analyzers (40-800 DEG C, 10 DEG C/min, N2) to above-mentioned step
Suddenly the luminous polypropylene acid first of the polyhedral oligomeric silsesquioxane Rare Earth Europium Complex of function containing esters of acrylic acid obtained by (2)
The heat endurance of ester is characterized, using pure PMA as control, the results showed that the Quito of function containing esters of acrylic acid
Initial decomposition temperature of the luminous polypropylene acid methyl esters of face body oligomeric silsesquioxane Rare Earth Europium Complex than virgin pp acid methyl esters
Degree is high, and decomposition curve also more slowly, has been indicated above the polyhedral oligomeric silsesquioxane rare-earth europium of function containing esters of acrylic acid
The luminous polypropylene acid methyl esters of complex is better than the heat endurance of virgin pp acid methyl esters.
Esters of acrylic acid work(using HITACHI F-7000 types XRFs to the gained obtained by above-mentioned steps (1)
The polyhedral of function containing esters of acrylic acid obtained by energy polyhedral oligomeric silsesquioxane Rare Earth Europium Complex and step (2) is low
The luminous polypropylene acid methyl esters of polysilsesquioxane Rare Earth Europium Complex is measured.As a result the propylene obtained by step (1) is shown
The base of function containing esters of acrylic acid obtained by esters of gallic acid function polyhedral oligomeric silsesquioxane Rare Earth Europium Complex and step (2)
There is the characteristic emission peak of europium ion in the luminous polypropylene acid methyl esters of polyhedral oligomeric silsesquioxane Rare Earth Europium Complex.
Embodiment 5
A kind of luminous polypropylene acids of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The synthetic method of material, including step are as follows：
(1) preparation of esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding
0.381g europium nitrates are put into measuring cup, add 20mL tetrahydrofurans, agitating solution to europium nitrate is completely dissolved
Afterwards, the methyl acrylate base oligomeric silsesquioxanes of 0.565g eight, ten methyl acrylate base oligomeric silsesquioxanes and 12 are weighed
The mixture of methyl acrylate base oligomeric silsesquioxane, stirs 1-10h at room temperature, and the reaction solution rotary evaporation of gained obtains
To compound be esters of acrylic acid function polyhedral oligomeric silsesquioxane Rare Earth Europium Complex.
(2) the luminous polypropylene acids material of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding
The preparation of material
Esters of acrylic acid function polyhedral oligomeric silsesquioxane rare-earth europium obtained by 0.05g steps (1) is coordinated
Thing is dissolved in 1mL tetrahydrofurans, is then added into 1.00g methacrylate monomers, and 5-10min is stirred at room temperature, decompression
Solvent is removed, 0.02g benzoyl peroxides is added, carries out bulk polymerization in situ.Polymerization process is in forced air drying
60 DEG C of holdings 2h, 70 DEG C of holdings 2h, 90 DEG C of holdings 36h, 100 DEG C of holding 1h in case.Finally give and transparent contained acrylate
The luminous polypropylene acid methyl esters of class function polyhedral oligomeric silsesquioxane Rare Earth Europium Complex.
Using Bruker TENSOR-27 types infrared absorption spectrometers to the esters of acrylic acid function obtained by above-mentioned steps (1)
The polyhedral oligomeric of function containing esters of acrylic acid obtained by polyhedral oligomeric silsesquioxane Rare Earth Europium Complex and step (2)
The structure of the luminous polypropylene acid methyl esters of silsesquioxane Rare Earth Europium Complex is characterized, as a result europium nitrate and esters of acrylic acid
The characteristic peak of function polyhedral oligomeric silsesquioxane can show, and be indicated above esters of acrylic acid function polyhedral oligomeric
Silsesquioxane is successfully coordinated with europium nitrate.
Using Mettler-Toledo TGA/DSC thermal gravimetric analyzers (40-800 DEG C, 10 DEG C/min, N2) to above-mentioned step
Suddenly the luminous polypropylene acid first of the polyhedral oligomeric silsesquioxane Rare Earth Europium Complex of function containing esters of acrylic acid obtained by (2)
The heat endurance of ester is characterized, using pure PMA as control, the results showed that the Quito of function containing esters of acrylic acid
Initial decomposition temperature of the luminous polypropylene acid methyl esters of face body oligomeric silsesquioxane Rare Earth Europium Complex than virgin pp acid methyl esters
Degree is high, and decomposition curve also more slowly, has been indicated above the polyhedral oligomeric silsesquioxane rare-earth europium of function containing esters of acrylic acid
The luminous polypropylene acid methyl esters of complex is better than the heat endurance of virgin pp acid methyl esters.
Using HITACHI F-7000 types XRFs to esters of acrylic acid function Quito obtained by above-mentioned steps (1)
The polyhedral oligomeric sesquialter of function containing esters of acrylic acid obtained by face body oligomeric silsesquioxane Rare Earth Europium Complex and step (2)
The luminous polypropylene acid methyl esters of siloxanes Rare Earth Europium Complex is measured.As a result the esters of acrylic acid obtained by step (1) is shown
The polyhedral of function containing esters of acrylic acid obtained by function polyhedral oligomeric silsesquioxane Rare Earth Europium Complex and step (2)
There is the characteristic emission peak of europium ion in the luminous polypropylene acid methyl esters of oligomeric silsesquioxane Rare Earth Europium Complex.
In summary, one kind function containing esters of acrylic acid polyhedral oligomeric silsesquioxane rare earth compounding of the invention
Luminous polypropylene acrylic materials synthetic method, the luminous polypropylene acrylic materials (polymethyl methacrylate and poly- of synthesis
Methyl acrylate) have good translucency and photo and thermal stability and synthetic method simple and easy to control.
Finally illustrate, above example is merely to illustrate technical scheme and unrestricted.It is familiar with this area
The personnel of technology obviously easily can carry out various improvement to these embodiments, and General Principle described herein is applied to
Without by performing creative labour in other embodiment.Therefore, the invention is not restricted to embodiment here, this area it is common
Technical scheme can be modified by technical staff or equivalent substitution, without departing from the ancestor of technical solution of the present invention
Purport and scope, it all should cover in scope of the presently claimed invention.
Claims (6)
- A kind of 1. luminous polypropylene acids material of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding The synthetic method of material, including step are as follows：（1）Rare earth nitrades are dissolved into organic solvent, add esters of acrylic acid function polyhedral oligomeric silsesquioxane, 1-10 h are stirred at room temperature, by the reaction solution rotary evaporation of gained, obtain esters of acrylic acid function polyhedral oligomeric silsesquioxane Alkane rare earth compounding；Described rare earth nitrades are terbium nitrate, europium nitrate, neodymium nitrate or dysprosium nitrate；Described esters of acrylic acid function polyhedral oligomeric silsesquioxane is methyl acrylate polyhedral oligomeric sesquialter silicon Oxygen alkane or methyl methacrylate polyhedral oligomeric silsesquioxane；The mol ratio of esters of acrylic acid function polyhedral oligomeric silsesquioxane and rare earth nitrades is 1: 0.1-2.5；（2）By step（1）Resulting esters of acrylic acid function polyhedral oligomeric silsesquioxane rare earth compounding, which is dissolved in, to be had Solvent, it is then added in acrylic monomer, 5-10 min is stirred at room temperature, removal of solvent under reduced pressure, add initiator, carry out Bulk polymerization in situ, is produced.
- 2. the hair of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding according to claim 1 The synthetic method of light polyacrylic materials, it is characterised in that step（1）Described in methyl acrylate polyhedral oligomeric times Half siloxanes is eight methyl acrylate base oligomeric silsesquioxanes, ten methyl acrylate base oligomeric silsesquioxanes or/and 12 Methyl acrylate base oligomeric silsesquioxane, methyl methacrylate polyhedral oligomeric silsesquioxane are prestox acrylic acid Carbomethoxy oligomeric silsesquioxane, decamethyl methyl acrylate base oligomeric silsesquioxane or/and ten methyl methacrylates Base oligomeric silsesquioxane.
- 3. the hair of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding according to claim 1 The synthetic method of light polyacrylic materials, it is characterised in that step（2）Described in acrylic monomer be acrylic compounds One or both of compound and its ester are mixed above.
- 4. the hair of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding according to claim 1 The synthetic method of light polyacrylic materials, it is characterised in that step（2）Described in esters of acrylic acid function polyhedral it is low The mass percent of polysilsesquioxane rare earth compounding and acrylic monomer is 1-15%:100%.
- 5. the hair of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding according to claim 1 The synthetic method of light polyacrylic materials, it is characterised in that step（2）Described in initiator for azodiisobutyronitrile or The mass percent of benzoyl peroxide and all initiators that can trigger radical polymerization, initiator and acrylic monomer For 2%：100%.
- 6. the hair of the polyhedral oligomeric of function containing esters of acrylic acid silsesquioxane rare earth compounding according to claim 1 The synthetic method of light polyacrylic materials, it is characterised in that step（2）Situ bulk polymerization process is：In 60 DEG C Keep 2 h, 70 DEG C of holdings 2 h, 90 DEG C of holdings 36 h, 100 DEG C of 1 h of holding.
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