CN117417511A - Terpolymer containing bicyclo [1.1.1] pentane and application of optical resin thereof - Google Patents
Terpolymer containing bicyclo [1.1.1] pentane and application of optical resin thereof Download PDFInfo
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- 230000003287 optical effect Effects 0.000 title claims abstract description 13
- 239000011347 resin Substances 0.000 title claims abstract description 11
- 229920005989 resin Polymers 0.000 title claims abstract description 11
- 229920001897 terpolymer Polymers 0.000 title abstract description 29
- MKCBRYIXFFGIKN-UHFFFAOYSA-N bicyclo[1.1.1]pentane Chemical compound C1C2CC1C2 MKCBRYIXFFGIKN-UHFFFAOYSA-N 0.000 title description 5
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 230000002950 deficient Effects 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 7
- 229920001577 copolymer Polymers 0.000 abstract description 7
- 229920005603 alternating copolymer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 239000004926 polymethyl methacrylate Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OAOSXODRWGDDCV-UHFFFAOYSA-N n,n-dimethylpyridin-4-amine;4-methylbenzenesulfonic acid Chemical compound CN(C)C1=CC=NC=C1.CC1=CC=C(S(O)(=O)=O)C=C1 OAOSXODRWGDDCV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920006125 amorphous polymer Polymers 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 description 1
- WBBPRCNXBQTYLF-UHFFFAOYSA-N 2-methylthioethanol Chemical compound CSCCO WBBPRCNXBQTYLF-UHFFFAOYSA-N 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- UBJVUCKUDDKUJF-UHFFFAOYSA-N Diallyl sulfide Natural products C=CCSCC=C UBJVUCKUDDKUJF-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- MTCMFVTVXAOHNQ-UHFFFAOYSA-N ethyl 2-(bromomethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CBr MTCMFVTVXAOHNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 150000003153 propellanes Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/57—Physical properties photorefractive, e.g. change of refractive index
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a novel double ring-containing (1.1.1)]A terpolymer of pentane and an optical resin application thereof. The terpolymer has the structure shown in formula I, wherein R 1 And R is R 2 R is cyclic or independent of each other 1 And R is R 2 Contains at least one electron withdrawing group, R 3 Is a hydrogen atom, an alkyl group or a hydroxyalkyl group, R 4 Is an electron withdrawing group and contains sulfur, and x and y represent the degree of polymerization. By [1.1.1]The main chain of the copolymer of the propeller alkane and two electron-deficient vinyl monomers contains bicyclo [1.1.1]The pentane structure of the alternating copolymer eliminates the head-head structure, and obviously improves the thermal stability; the copolymer has high refractive index, abbe number and good transparency, and the glass transition temperature can be adjusted by changing the structure of the vinyl monomer and the relative proportion of the two vinyl monomers, so that the copolymer is a good transparent optical resin material.
Description
Technical Field
The invention relates to optical resin and a preparation method thereof, in particular to a terpolymer containing bicyclo [1.1.1] pentane, which is prepared by copolymerization reaction, can be applied as optical resin, and belongs to the fields of polymer chemistry and physics.
Background
Polymethyl methacrylate (PMMA) is commonly known as organic glass, is a commercial optical resin, has good transparency in a visible light region, but PMMA prepared by common free radical polymerization has poor thermal stability due to the fact that the PMMA contains a head-head structure with low dissociation energy [ Kashiwagi, T.et al. Macromolecules 1986,19,2160-2168 ]. The preparation of polymer blends or the addition of nanoparticles can improve the thermal stability of PMMA to some extent, but these methods can lead to problems of poor polymer compatibility and nanoparticle agglomeration [ Parameswaranpilari, J.et al.J.appl.Polym.Sci.2016,133,43628 ]. The incorporation of aliphatic rings (e.g., adamantane) in pendant polymer groups is also an effective strategy to improve the thermal stability of polymers, but this approach has very limited improvement in thermal stability [ Zhong, f.et al, colloid Surface a 2019,578,123594 ]. The introduction of sulfur-containing groups in the PMMA side groups can raise the refractive index, but can significantly reduce the abbe number [ Do, j.y.et. Act.function.polym.2015, 91-92,28-34 ]. The polymer with the main chain containing the bridged ring structure synthesized by the thio-ene reaction has better thermal stability and optical property, but a highly toxic monomer [ Ueda, M.et al. Macromolecules 2012,45,3402-3408 ] is used in the synthesis. Therefore, these methods are difficult to be practically applied.
Disclosure of Invention
The invention aims to provide a transparent optical resin with good thermal stability, higher refractive index and Abbe number, which is prepared by using easily available raw materials in a high-efficiency and controllable manner.
In a first aspect of the present invention, there is provided a polymer comprising a bicyclo [1.1.1] pentane structure having the structure shown in formula I:
in the formula I, R 1 And R is R 2 Can be cyclic or independent, R 1 And R is R 2 At least one of which is an electron withdrawing group (e.g., an ester group, etc.); r is R 3 Is a hydrogen atom, an alkyl group or a hydroxyalkyl group, R 4 Is an electron withdrawing group (e.g., an ester group, etc.) and contains a sulfur element; x, y represent the degree of polymerization and x/y represent the ratio of two different structural units in the copolymer.
Preferably, when R 1 And R is R 2 R, independently of one another, is 1 Can be a hydrogen atom, an alkyl group or a hydroxyalkyl group, preferably a hydrogen atom, a C1-C6 alkyl group, a C1-C6 hydroxyalkyl group; r is R 2 Are electron withdrawing groups, typically electron withdrawing groups such as ester groups, acyl groups, sulfone groups, cyano groups, for example: ester group-COOR, acyl group-C (=O) -R, sulfonyl group-S (=O) 2 R, wherein R is preferably C1-C6 alkyl or phenyl.
When R is 1 And R is R 2 When ring-formed, one of the following groups (wavy line represents bond) may be selected:
R 3 selected from the group consisting of hydrogen atoms, C1-C6 alkyl groups, C1-C6 hydroxyalkyl groups, such as methyl, ethyl, hydroxymethyl, hydroxyethyl, and the like.
Preferably, R 4 May be selected from one of the following groups: COO- (CH) 2 ) m -S-C n H 2n+1 ，-COO-(CH 2 ) m -S(＝O) 2 -C n H 2n+1 ，-S(＝O) 2 -C n H 2n+1 ，-S(＝O) 2 -Ph, wherein m, n are each independently integers from 1 to 6, ph being phenyl; or one of the following groups:
preferably, x/y is 0.1 to 10.
In a second aspect of the present invention, a method for synthesizing the polymer of formula I by ternary polymerization of [1.1.1] propeller alkane and two electron-deficient vinyl monomers is provided, as follows:
wherein R is 1 、R 2 、R 3 、R 4 As previously mentioned, monomer 1 and monomer 2 are not identical.
Monomer 1 may be selected from one of the following compounds, which are essentially characterized by containing electron-deficient double bonds:
the monomer 2 can be selected from one of the following compounds, and is basically characterized by containing electron-deficient double bonds and sulfur:
two electron-deficient vinyl monomers are copolymerized with [1.1.1] propeller alkane, and the polymerization reaction is stopped when three monomers are remained, so that the terpolymer with an alternate structure is obtained. Generally, the polymerization reaction does not require an initiator, and the polymerization temperature is in the range of 20 to 40 ℃, preferably 35 ℃ and the polymerization time is 6 to 24 hours. The polymerization time is preferably 7 hours when the monomer 1 is an acyclic monomer, and preferably 24 hours when the monomer 1 is a cyclic monomer.
In the third aspect of the present invention, based on the above-mentioned polymer of formula I having good thermal stability, high refractive index and abbe number, the polymer of formula I can be used as a transparent optical resin material for manufacturing lenses, camera lenses, prisms, waveguides, diffraction gratings, touch screens, display screens, etc.
Compared with the prior art, the invention has the following technical advantages:
1. the alternating copolymer with the main chain containing the bicyclo [1.1.1] pentane structure is obtained by copolymerizing the [1.1.1] propeller alkane and two vinyl monomers, the head-head structure is eliminated, and the thermal stability of the polymer is obviously improved.
2. Two different vinyl monomers are copolymerized with [1.1.1] propeller alkane to obtain two amorphous polymers with random repeating unit sequences, the copolymers have good transparency, and the glass transition temperature can be adjusted by changing the structure of the vinyl monomers and the relative proportion of the two vinyl monomers.
3. Using vinyl monomers containing heavy elements (e.g., sulfur, etc.), polymers with higher refractive indices are obtained while the Abbe number remains high.
Detailed Description
The following describes in detail the preparation process of the optical resin of the present invention by way of examples, but does not limit the scope of the present invention in any way.
For convenience of description, in the present invention, the term [1.1.1]]Propeller (1.1.1)]Propellane) is abbreviated as P, methyl methacrylate is abbreviated as M, ethyl 2- (methylthio) acrylate is abbreviated as A, and the cyclic allylthioether monomer 6-methylene-1, 4-oxathiophen-7-one is abbreviated as B, bicyclo [ 1.1.1.1]Pentane (dicycloheo [ 1.1.1)]pentane) is abbreviated as BCP, and 4- (dimethylamino) pyridine p-toluenesulfonate is abbreviated as DPTS. Using M separately a A b P and B a A b P identifies the terpolymer and the subscripts a, b in the polymer name represent the feed equivalent of the vinyl monomer (1 equivalent of monomer P) at the time of synthesizing the polymer, respectively.
Example 1 preparation of monomer A
The 250mL round bottom flask equipped with the magneton was placed in vacuum and repeated with 3 times of vacuum-nitrogen addition, 5mL of 2- (methylthio) ethanol (57.5 mmol,1 equiv), 9.7mL of triethylamine (69 mmol,1.2 equiv) and 60mL of Dichloromethane (DCM). The reaction flask was placed in an ice-water bath and 4.7mL of acryloyl chloride (57.5 mmol,1 equiv) was added. The ice-water bath was removed and reacted at room temperature for 2 hours. Adding saturated sodium chloride solution, and separating; the aqueous phase was extracted with dichloromethane. The organic phases were combined and then taken up in anhydrous Na 2 SO 4 And (5) drying. The solvent was removed by rotary evaporation and column chromatography (petroleum ether/ethyl acetate=19/1, volume ratio) gave 7.48g of the product (89% yield). 1 H NMR(400MHz,CDCl 3 ,δ):6.42(dd,J＝17.3,1.4Hz,1H),6.12(dd,J＝17.3,10.4Hz,1H),5.84(dd,J＝10.5,1.4Hz,1H),4.32(t,J＝6.9Hz,2H),2.76(t,J＝6.9Hz,2H),2.16(s,3H).
Example 2 preparation of monomer B
A250 mL round bottom flask equipped with a magnet was placed in a vacuum line and repeated with vacuum-nitrogen 3 times, 5mL 2-mercaptoethanol (72 mmol,1 equiv), 10mL triethylamine (72 mmol,1 equiv) and 70mL dichloromethane were added. 10mL of ethyl 2- (bromomethyl) acrylate (72 mmol,1 equiv) was added dropwise with stirring and reacted for 20 minutes. After adding water, the mixture was separated, and the aqueous phase was extracted with dichloromethane. The organic phases were combined and then taken up in anhydrous Na 2 SO 4 Drying and spin-evaporating to remove the solvent. The resulting crude product was dissolved in 20mL of methanol, transferred to a 250mL round bottom flask, and the magneton was added. 3.2g sodium hydroxide (79.2 mmol,1.1 equiv) was dissolved in 100mL water and added to the reaction flask with stirring. The reaction solution was acidified to ph=2 with hydrochloric acid and extracted with ethyl acetate. By anhydrous Na 2 SO 4 After drying the organic phase, the solvent was removed by rotary evaporation to give the crude hydroxy acid product. In a 500mL round bottom flask, 6.2g EDC. HCl (32.1 mmol,1.3 equiv) and 1.5g 4- (dimethylamino) pyridine p-toluenesulfonate (DPTS) (4.9 mmol,0.2 equiv) were weighed out, dissolved in 100mL dichlorohexane and the magneton was added. 4g of hydroxy acid (24.7 mmol,1 equiv) was dissolved in 50mL of dichloromethane and added dropwise to the reaction flask over 12 hours. Adding saturated sodium chloride solution, and separating; the aqueous phase was extracted with dichloromethane. The organic phases were combined and then taken up in anhydrous Na 2 SO 4 Drying and spin-evaporating to remove the solvent. Column chromatography (petroleum ether/ethyl acetate=3/1, volume ratio) gave 2.08g of product (58% of total yield of three steps). 1 H NMR(400MHz,CDCl 3 ,δ):5.79(s,1H),5.55(d,J＝1.2Hz,1H),4.49–4.39(m,2H),3.37–3.25(m,2H),2.98–2.84(m,2H).
Example 3 terpolymer M 0.75 A 2.25 Synthesis of P
1.02g of monomer A (6.975 mmol,2.25 equiv) was weighed into a 25mL Schlenk tube fitted with a magnet and the vacuum line was switched on to repeat the vacuum-nitrogen charging 3 timesUnder nitrogen protection, 5mL of [1.1.1 is added]Propeller diethyl ether solution (0.62 mol/L,3.1mmol,1 equiv) and 247. Mu.L of methyl methacrylate (M) (2.325 mmol,0.75 equiv). The Schlenk tube was placed in an oil bath at 35℃for 7 hours for polymerization. Dropping the reaction solution into methanol, centrifuging, removing supernatant, dissolving polymer with chloroform, dropping into methanol for precipitation, repeating the dissolving-precipitating process for 2 times, and vacuum drying at 50deg.C to remove residual solvent to obtain M 0.75 A 2.25 P white solid 641mg (44% yield, calculated as 100% conversion for all monomers without regard to monomer conversion). The ratio of different structural units in the polymer can be obtained through the integral proportion of the peak area in the nuclear magnetic resonance hydrogen spectrum. The sum of the number of structural units derived from the two vinyl monomers is equal to the number derived from [1.1.1]]The number of structural units of the propeller alkane indicates that the terpolymer consists of two alternating repeat units. The feeding amount of the monomers A and M is changed, and other conditions are the same, so that M with different compositions is obtained a A b P. The relative feeding ratio (a/b is increased) of the monomer M is improved, and the terpolymer (x/y is larger) with higher content of methyl methacrylate structural units can be obtained.
The thermal stability of the terpolymer was characterized by thermogravimetric analysis (TGA). These terpolymers all have good thermal stability, their 5% weight loss temperature is between 350 and 360 ℃ and far higher than PMMA (144 ℃). The terpolymers are all amorphous polymers, only glass transition is observed in Differential Scanning Calorimeter (DSC) tests, and polymers containing a higher proportion of methyl methacrylate structural units have a higher glass transition temperature. The amorphous terpolymers all have good transparency, and the ultraviolet-visible absorption and transmission spectra show that the terpolymers have no absorption peak in the ultraviolet-visible light band and have a transmittance of more than 91% at 550 nm. The refractive index and Abbe number of the terpolymer were measured using an ellipsometer. The refractive index of the ternary copolymer containing sulfur element is higher than that of PMMA. The sulfur content of the polymer depends on the relative proportion of the corresponding structural units of the two vinyl monomers, and the content of sulfur element in the copolymer can be improved by adding more monomer A, so that the polymer has higher refractive index. Polymer M 2.25 A 0.75 The refractive index of P at 589.3nm was 1.519 and the Abbe number was 51.9; m having a higher sulfur content 0.75 A 2.25 The refractive index of P was 1.534 and the Abbe number was reduced to 41.1.
Example 4, terpolymer B 1 A 2 Synthesis of P
0.34g of monomer A (2.4 mmol,2 equiv) was weighed into a 10mL Schlemk tube fitted with a magnet and the vacuum-nitrogen-sparged 3 times was repeated with a vacuum line. 0.18g of monomer B (1.2 mmol,1 equiv) are weighed in a vial with 2mL of [1.1.1]After dissolution of the propeller ethereal solution (0.6 mol/L,1.2mmol,1 equiv) the Schlenk tube was added. The Schlenk tube was placed in an oil bath at 35℃for polymerization for 24 hours. Dropping the reaction liquid into methanol, centrifuging, removing supernatant, dissolving polymer with chloroform, dropping into methanol for precipitation, repeating the dissolving-precipitating process for 2 times, and vacuum drying at 50deg.C to remove residual solvent to obtain B 1 A 2 P white solid 255mg (43% yield, calculated as 100% conversion for all monomers without regard to monomer conversion). The ratio of different structural units in the polymer can be obtained through the integral proportion of the peak area in the nuclear magnetic resonance hydrogen spectrum. The sum of the number of structural units derived from the two vinyl monomers is equal to the number derived from [1.1.1]]The number of structural units of the propeller alkane indicates that the terpolymer consists of two alternating repeat units. Changing the feeding amount of the monomers B and A, and obtaining B with different compositions under the same other conditions a A b P. And the relative feeding ratio (a/B is increased) of the monomer B is improved, so that the terpolymer with higher cyclic side group content can be obtained.
The thermal stability of the terpolymer was characterized by thermogravimetric analysis (TGA). These terpolymers all have good thermal stability, their 5% weight loss temperature is around 340 ℃ and far higher than PMMA (144 ℃). The terpolymer is an amorphous polymer, only glass transition is observed in a Differential Scanning Calorimeter (DSC) test, the content of the cyclic side group can be improved by increasing the doping proportion of the monomer B, and the corresponding polymer hasHigher glass transition temperature. B due to the presence of a pendant rigid lactone ring structure a A b Terpolymer ratio of P series M a A b The terpolymers of the P series have higher glass transition temperatures. The amorphous terpolymers all have good transparency, and the ultraviolet-visible absorption and transmission spectra show that the terpolymers have no absorption peak in the visible light band and have a transmittance of more than 98% at 550 nm. The refractive index and Abbe number of the terpolymer were measured using an ellipsometer. The refractive index of the ternary copolymer containing sulfur element is higher than that of PMMA. Since monomer B and monomer a have similar chemical compositions, the terpolymer has a fixed sulfur content (15.2 wt%). Thus, when the relative proportions of the structural units corresponding to the two vinyl monomers are changed, the refractive index of the polymer is not changed substantially, and is about 1.55, which is higher than M with low sulfur content a A b P series.
TABLE 1 copolymer M a A b P and B a A b Thermal and optical Properties of P
a Tetrahydrofuran phase GPC measurement; b x/y is the ratio of the two repeating units in the terpolymer, consisting of 1 H NMR integral proportion is obtained; c TGA assay, T d,5％ Is the temperature at which the mass loss of the sample is 5%; d t as determined by DSC g The glass transition temperature is the glass transition temperature of the second heating process; e the transmittance of the polymer film at 550 nm; f determination of n by ellipsometry D ，n F ，n C Refractive indices, v, of the polymer film at 589.3nm,486.1nm and 656.3nm, respectively D Is the Abbe number of the polymer film, and is expressed by the formula v D ＝(n D -1)/(n F -n C ) And (5) calculating to obtain the product.
Claims (10)
1. A polymer of formula I:
in the formula I, R 1 And R is R 2 Is cyclic or independent of each other, and R 1 And R is R 2 At least one of them is an electron withdrawing group; r is R 3 Is a hydrogen atom, an alkyl group or a hydroxyalkyl group, R 4 Is an electron withdrawing group and contains a sulfur element; x and y represent the degree of polymerization.
2. The polymer of formula I of claim 1 wherein when R 1 And R is R 2 R, independently of one another, is 1 Is a hydrogen atom, an alkyl group or a hydroxyalkyl group, R 2 An electron withdrawing group selected from the group consisting of an ester group, an acyl group, a sulfone group, and a cyano group; when R is 1 And R is R 2 When forming a ring, one of the following groups is selected:
3. the polymer of formula I of claim 1 wherein R 4 One selected from the following groups:
-COO-(CH 2 ) m -S-C n H 2n+1 ，-COO-(CH 2 ) m -S(＝O) 2 -C n H 2n+1 ，-S(＝O) 2 -C n H 2n+1 ，-S(＝O) 2 -Ph, wherein m, n are each independently integers from 1 to 6, ph being a benzene ring; alternatively, R 4 One selected from the following groups:
4. the polymer of formula I of claim 1 wherein x/y is from 0.1 to 10.
5. A polymer of formula I according to claim 1, selected from one of the following:
6. the process for preparing the polymer of formula I as defined in claim 1, which comprises the step of ternary polymerization of [1.1.1] propeller alkane and two electron-deficient vinyl monomers, wherein the process comprises the following steps:
wherein R is 1 、R 2 、R 3 、R 4 As stated in claim 1, monomer 1 and monomer 2 are not identical.
7. The process according to claim 6, wherein monomer 1 is selected from one of the following compounds:
8. the process according to claim 6, wherein monomer 2 is selected from one of the following compounds:
9. the process according to claim 6, wherein the polymerization of the [1.1.1] propeller with the two monomers does not require an initiator, and the polymerization temperature is 20 to 40℃and the polymerization time is 6 to 24 hours.
10. Use of a polymer of formula I according to any one of claims 1 to 5 as an optical resin.
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