CN108948349B - Spiro-ring polymer material and preparation method thereof - Google Patents
Spiro-ring polymer material and preparation method thereof Download PDFInfo
- Publication number
- CN108948349B CN108948349B CN201810861656.0A CN201810861656A CN108948349B CN 108948349 B CN108948349 B CN 108948349B CN 201810861656 A CN201810861656 A CN 201810861656A CN 108948349 B CN108948349 B CN 108948349B
- Authority
- CN
- China
- Prior art keywords
- monomer
- spiro
- polymer material
- preparation
- polymeric material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to the technical field of polymer materials, in particular to a spiro polymer material and a preparation method thereof. The invention provides a novel spiro polymer material which has good solubility and can be fully dissolved in common organic solvents such as dichloromethane, trichloromethane, tetrahydrofuran, dimethyl sulfoxide and the like. The preparation method of the spiro-polymer material comprises the following steps: under the atmosphere of carbon dioxide, mixing and reacting a diisonitrile derivative monomer A and a symmetrical alkyne diester derivative monomer B to obtain an intermediate product; and adding the intermediate product into a precipitator to obtain a precipitate, and filtering and collecting the precipitate to obtain the spiro polymer material. The method is carried out in a carbon dioxide atmosphere, carbon dioxide is used as a monomer to participate in polymerization reaction, a catalyst is not needed, a polymerization system does not need to be dehydrated, polymerization is completed in one step by a one-pot method, the method is simple, and the yield is high.
Description
Technical Field
The invention relates to the technical field of polymer materials, in particular to a spiro polymer material and a preparation method thereof.
Background
Spiro-polymers are a class of high molecular materials containing Spiro rings, and have wide application in the fields of luminescent materials, medicines, asymmetric catalysis, pesticides, gas adsorption, high molecular adhesives and the like. In 2003, Endo et al (HinoT. and Endo T. macromolecules 2003,36,5902) produced spirocyclic monomers without volume shrinkage, in Sc (OTf)3Under the action of the (B) and phenyl glyceryl ether, a copolymer without volume shrinkage can be obtained, and the polymer has better mechanical property and thermal stability. However, this method requires synthesis of a spiro-containing monomer and polymerization, which increases the number of reaction steps and requires a metal catalyst for catalysis. In 2011, Han et al (Chen Q.; Wang J.X.; Wang Q.; Biann.; Li Z.H.; Yan C.G.and Han B.H.macromolecules 2011,44,7987) obtained a porous spiro polymer by reacting fluorene with alkyne and phenylboronic acid monomers in the presence of a palladium catalyst, which was specific for carbon dioxideHas good adsorption effect. The research on the spiro polymer mainly focuses on the fields of chemical modification, flame retardance, photoelectric application and the like.
The spiro polymer is a structural unit in which two cyclic structures share one atom, and is generally polymerized by preparing a monomer containing the spiro structure and then using a conventional polymerization method. The steps are complicated, a metal catalyst is generally needed for catalysis, the overall yield is low, and the rapid development of the spiro polymer materials is limited to a certain extent.
Therefore, it is necessary to develop a new method for preparing a spiro polymer material simply and efficiently.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a novel spiro polymer material, which has good solubility and is fully soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and dimethyl sulfoxide.
The second purpose of the invention is to provide a preparation method of the spiro polymer material, the preparation method is completed in one step, the reaction is carried out in the carbon dioxide atmosphere, no catalyst is needed, a polymerization system does not need to be dehydrated, the preparation method is simple, the conditions are mild, and the yield is high.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a spiro-polymer material having the formula:
wherein R is1Selected from aliphatic or aromatic functional groups, R2Selected from aliphatic functional groups, and n is an integer more than or equal to 1.
The spiro polymer material has good solubility, and can be fully dissolved in common organic solvents such as dichloromethane, trichloromethane, tetrahydrofuran, dimethyl sulfoxide and the like.
Preferably, said R is1The structure of (a) includes any one of:
preferably, said R is2Has the structure of-CxH2x+1(ii) a Wherein x is selected from an integer between 1 and 6.
Preferably, the weight average molecular weight of the spiro-polymer material is 1000-100000. More preferably, the weight average molecular weight of the spiro polymeric material is 4000-60000.
The invention also provides a preparation method of the spiro polymer material, which comprises the following steps:
under the atmosphere of carbon dioxide, mixing and reacting the monomer A and the monomer B to obtain an intermediate product;
adding the intermediate product into a precipitator to obtain a precipitate, and filtering and collecting the precipitate to obtain the spiro polymer material;
wherein the structural formula of the monomer A is
The R is1Selected from aliphatic or aromatic functional groups; the structural formula of the monomer B is
The R is2Selected from aliphatic functional groups.
The preparation method of the spiro polymer is carried out in a carbon dioxide atmosphere, carbon dioxide is used as a monomer to participate in polymerization reaction, a catalyst is not needed, a polymerization system does not need to be dehydrated, the polymerization is completed in one step by a one-pot method, the method is simple, and the yield is high.
Preferably, the molar ratio of monomer A to monomer B is 1: 1 (1.6-3), preferably 1: 2-3, more preferably 1: 2.4.
Preferably, monomer a, monomer B and solvent are mixed and reacted under carbon dioxide atmosphere to obtain an intermediate product. More preferably, the solvent comprises one or more of toluene, 1, 2-dichloroethane, 1, 4-xylene and 1, 4-dioxane, preferably toluene.
Preferably, the concentration of the monomer A in the solvent is 0.04-0.16 mol/L.
Preferably, the precipitant comprises one or two of n-hexane and petroleum ether, preferably n-hexane. More preferably, the intermediate product is slowly added to the precipitant while stirring.
Preferably, said R is1The structure of (a) includes any one of:
preferably, said R is2Has the structure of-CxH2x+1(ii) a Wherein x is selected from an integer between 1 and 6.
Preferably, the reaction temperature is 25-100 ℃, and the reaction time is 1-36 h. More preferably, the reaction temperature is 50-90 ℃, the reaction time is 6-18h, and even more preferably, the reaction temperature is 80 ℃, and the reaction time is 12 h.
When the reaction temperature is too low, the activity of the monomer A and the monomer B is insufficient, and the molecular weight and the yield of the polymer obtained by the reaction are not high; when the reaction is too high, the reaction has too many active centers, the reaction rate is too high, side reactions are increased, and the reaction is not favorable for proceeding.
Preferably, the spiro polymer material is obtained after filtering, collecting and drying the precipitate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the spiro polymer material has good solubility, and can be fully dissolved in common organic solvents such as dichloromethane, trichloromethane, tetrahydrofuran, dimethyl sulfoxide and the like;
(2) according to the preparation method of the spiro polymer material, the polymer is directly obtained through a one-pot method, a spiro monomer is not required to be synthesized firstly, a catalyst is not required to be added in the reaction, and the preparation method meets the requirement of green chemistry;
(3) the preparation method of the spiro polymer material has mild reaction conditions, does not need strict anhydrous conditions, and is simple to operate in a carbon dioxide atmosphere;
(4) the preparation method of the spiro polymer can prepare the polymer with the polyester group containing the spiro main chain structure, and has good adaptability; when the spiro polymer is prepared by the method, the molecular structure and the molecular weight are regulated and controlled by regulating and controlling the monomer type, the monomer concentration, the molar ratio, the solvent, the reaction temperature, the reaction time and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an infrared spectrum of a spiro polymer material P1a2a-2, P1a2a-1, P1b2a-1, P1b2a-2, P1e2a-1 and P1f2a-2 prepared in examples 2, 3, 4, 5, 8 and 10 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum diagram of the spiro polymer materials P1a2a-2, P1a2a-1, P1b2a-1, P1b2a-2, P1e2a-1 and P1f2a-2 prepared in examples 2, 3, 4, 5, 8 and 10 of the present invention;
FIG. 3 shows nuclear magnetic carbon spectra of spiro polymer materials P1a2a-2, P1a2a-1, P1b2a-1, P1b2a-2, P1e2a-1 and P1f2a-2 prepared in examples 2, 3, 4, 5, 8 and 10 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a spiro polymer material, which has the following structural formula:
wherein R is1Selected from aliphatic or aromatic functional groups, R2Selected from aliphatic functional groups, and n is an integer more than or equal to 1.
The invention also provides a preparation method of the spiro polymer material, which comprises the following steps:
under the atmosphere of carbon dioxide, mixing and reacting the monomer A and the monomer B to obtain an intermediate product;
adding the intermediate product into a precipitator to obtain a precipitate, and filtering and collecting the precipitate to obtain the spiro polymer material;
wherein the structural formula of the monomer A is
The R is1Selected from aliphatic or aromatic functional groups; the structural formula of the monomer B is
The R is2Selected from aliphatic functional groups.
In a preferred embodiment of the present invention, R is1The structure of (a) includes any one of:
in a preferred embodiment of the present invention, R is2Has the structure of-CxH2x+1(ii) a Wherein x is selected from an integer between 1 and 6.
The preparation method of the spiro polymer material has the following specific reaction formula:
the present invention will be described in detail below by way of specific examples.
In the following examples, the weight average molecular weight and the molecular weight distribution were determined by means of a Gel Permeation Chromatograph (GPC) of Waters1515isocratic HPLC pump, WATERS, USA, with tetrahydrofuran as the mobile phase, narrow-distribution polystyrene as the standard and a measurement temperature of 25 ℃. The NMR results were determined by AV 400 NMR spectrometer purchased from Bruker. The infrared spectrum was measured by Brookfield (ALPHA) spectroscopy.
Example 1
This example provides the monomer a and its preparation method, where the structural formula of the monomer a is:
the preparation method of the monomer A comprises the following steps: adding 50mmol of reactant C, 136mg of benzyl triethyl ammonium bromide, 8mL of trichloromethane and 30mL of dichloromethane into a reaction bottle, stirring for 15min at room temperature, slowly adding 30g of a 50% sodium hydroxide aqueous solution, reacting for 12h at 40 ℃, washing, extracting for three times by using 100mL of dichloromethane, collecting an organic phase, drying by using anhydrous magnesium sulfate, carrying out suction filtration, collecting the organic phase, concentrating, and carrying out column chromatography separation by using petroleum ether/dichloromethane as an eluent to obtain a monomer A; specific species of reactant C, R1And the monomer A obtained by the preparation is shown in the following Table 1.
TABLE 1 kinds of reactants C and corresponding monomers A
Wherein, the structural characterization analysis of each monomer A is as follows:
monomer A1: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3): δ — 3.80(s, 2H), 2.02-1.99(d, 4H), 1.76-1.74(d, 4H); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：156.21，156.16，156.11，49.66，49.60，49.55，26.86。
monomer A2: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3): δ 6.91(s, 4H), 3.92(s, 2H), 2.78-2.72(q, 8H), 1.26-1.22(t, 12H); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：167.92，141.51，141.06，126.82，41.53，25.87，13.97。
monomer A3: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3): δ 6.90-6.89(d, 4H), 3.87(s, 2H), 2.77-2.71(q, 4H), 2.38(s, 6H), 1.26-1.22(t, 6H); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：167.73，141.27，140.93，135.35，128.29，126.78，41.36，25.83，19.02，13.97。
monomer A4: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3): δ — 3.90(s), 3.37-3.33(t), 2.17-2.14(d), 1.96-1.92(d), 1.76-1.73(d), 1.61-1.50(q), 1.36-1.33(q), 1.21(s), 1.13(s), 1.07-1.03(t), 0.92-0.84 (q); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：154.94，154.89，154.83，154.78，153.86，153.81，153.76，153.70，52.31，52.26，52.20，52.14，50.66，50.61，50.56，50.51，43.58，43.42，43.17，33.34，33.29，33.26，33.04，32.94，32.73，30.94，30.61，30.59，27.00。
monomer A5: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3)：δ＝7.39(s, 4H), 4.66(s, 4H); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：158.26，158.21，158.16，132.75，121.31，45.27，45.19，45.12。
monomer A6: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3): δ 7.40-7.38(d, 4H), 7.03-7.01(d, 4H); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：164.36，156.69，128.32，119.76。
monomer A7: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3): δ -8.01-7.99 (d, 4H), 7.55-7.53(d, 4H); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：169.13，141.54，129.39，127.67。
monomer A8: in the nuclear magnetic hydrogen spectrum, the magnetic flux density of the magnetic material,1H NMR(400MHz，CDCl3): δ -7.79-7.77 (d, 2H), 7.40-7.36(m, 2H), 7.29(s, 4H), 7.24-7.22(d, 4H), 7.18-7.16(d, 4H); in the nuclear magnetic carbon spectrum,13C NMR(100MHz，CDCl3)：164.63，149.37，146.84，140.13，129.02，128.41，128.30，126.54，125.81，120.73，64.94。
example 2
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
The monomer B is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 134mg of monomer A, 408mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12 hours in a carbon dioxide atmosphere, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1a2a-2 with the yield of 73.0%.
The prepared spiro polymer material P1a2a-2 is characterized by the following data:
the infrared spectrum is shown in FIG. 1(A), and the infrared peak is (cm)-1)：3291，2836，1619，1509，1356，1244，1178，1109，1031，974，546；
The nuclear magnetic hydrogen spectrum is shown in FIG. 2(A),1H NMR(400MHz，CDCl3)：4.45-4.23，3.65，1.88-1.25；
the nuclear magnetic carbon spectrum is shown in FIG. 3(A),13C NMR(100MHz，CDCl3)：160.96，159.47，159.14，151,23，158.33，151.34，147.81，145.41，140.05，136.28，111.48，63.17-62.53，56.24，31.66-30.62，14.00，13.69；
GPC measured the weight average molecular weight MW19800, MWD 2.00.
Example 3
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
The monomer B is
The preparation method of the spiro polymer material was referred to that of example 2, except that the kind of the monomer B was replaced, and the amount of the monomer B added was 341 mg. The obtained spiro-polymer material P1a2a-1 was prepared with a yield of 80.9%.
The prepared spiro polymer material P1a2a-1 is characterized, the infrared spectrum is shown as figure 1(B), the nuclear magnetic hydrogen spectrum is shown as figure 2(B), and the nuclear magnetic carbon spectrum is shown as figure 3 (B).
GPC measured the weight average molecular weight MW25400, MWD of 3.02.
Example 4
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
monomer A is
Monomer B is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 330mg of monomer A, 341mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12 hours in a carbon dioxide atmosphere, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) and dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1b2a-1 with the yield of 76.8%.
The prepared spiro polymer material P1b2a-1 is characterized in that an infrared spectrogram, a nuclear magnetic hydrogen spectrogram and a nuclear magnetic carbon spectrogram are respectively shown in figures 1(C) and 2(C) and 3 (C).
GPC measured the weight average molecular weight MW44300, MWD 4.03.
Example 5
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
monomer A is
Monomer B is
The preparation method of the spiro polymer material is referred to the preparation method of example 4, except that the kind of the monomer B is replaced, and the addition amount of the monomer B is 408 mg. The spiro polymer material P1b2a-2 was prepared in 70.2% yield.
The prepared spiro polymer material P1b2a-2 is characterized in that an infrared spectrogram, a nuclear magnetic hydrogen spectrogram and a nuclear magnetic carbon spectrogram are respectively shown in figures 1(D) and 2(D) and 3 (D).
GPC measured the weight average molecular weight MW25700, MWD 2.27.
Example 6
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
Monomer B is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 306mg of monomer A, 341mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12 hours in a carbon dioxide atmosphere, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1c2a-1 with the yield of 76.7%.
The prepared spiro polymer material P1c2a-1 is characterized, and an infrared spectrogram, a nuclear magnetic hydrogen spectrogram and a nuclear magnetic carbon spectrogram are similar to those in example 4.
GPC measured the weight average molecular weight MW18400, MWD 2.15.
Example 7
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
monomer A is
Monomer B is
The preparation method of the spiro polymer material was referred to that of example 6, except that the kind of the monomer B was replaced and the amount of the monomer B added was 408 mg. The spiro polymer material P1c2a-2 was prepared in 74.0% yield.
The prepared spiro polymer material P1c2a-2 is characterized, and an infrared spectrogram, a nuclear magnetic hydrogen spectrogram and a nuclear magnetic carbon spectrogram are similar to those in example 5.
GPC measured the weight average molecular weight MW22300, MWD 2.44.
Example 8
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
The monomer is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 230mg of monomer A, 341mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12 hours in the atmosphere of carbon dioxide, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1e2a-1 with the yield of 72.1%.
The prepared spiro polymer material P1E2a-1 is characterized, an infrared spectrogram, a nuclear magnetic hydrogen spectrogram and a nuclear magnetic carbon spectrogram are respectively shown in figures 1(E) and 2(E) and 3 (E).
GPC measured the weight average molecular weight MW169900, the molecular weight distribution is MWD 2.19.
Example 9
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
Monomer B is
The preparation method of the spiro polymer material was referred to that of example 8, except that the kind of the monomer B was replaced and the amount of the monomer B added was 408 mg. The spiro polymer material P1e2a-2 was prepared in 66.4% yield.
The prepared spiro polymer material P1e2a-2 is characterized, and the infrared spectrum, nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum are similar to the results of example 8.
GPC measured the weight average molecular weight MW12400, MWD 1.51.
Example 10
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
The monomer B is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 156mg of monomer A, 408mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12 hours in a carbon dioxide atmosphere, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1f2a-2 with the yield of 82.1%.
The prepared spiro polymer material P1F2a-2 is characterized in that an infrared spectrogram, a nuclear magnetic hydrogen spectrogram and a nuclear magnetic carbon spectrogram are respectively shown in figures 1(F) and 2(F) and 3 (F).
GPC measured the weight average molecular weight MW59000, molecular weight distribution MWD of 3.28.
Example 11
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
The monomer B is
The preparation of the spiro polymer material was carried out according to the preparation method of example 10, except that the monomer B was replaced and the amount of the monomer B added was 341 mg. The spiro polymer material P1f2a-1 was prepared with a yield of 87.7%.
The prepared spiro polymer material P1f2a-1 is characterized, and the infrared spectrum, nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum are similar to the results of the example 10.
GPC measured the weight average molecular weight MW6300, MWD 1.75.
Example 12
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
Monomer B is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 220mg of monomer A, 408mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12h in a carbon dioxide atmosphere, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) and dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1g2a-2 with the yield of 87.9%.
The prepared spiro polymer material P1g2a-2 is characterized, and the infrared spectrum, nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum are similar to the results of example 7.
GPC measured the weight average molecular weight MW11300, MWD 3.60.
Example 13
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
the monomer A is
Monomer B is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 268mg of monomer A, 408mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12 hours in a carbon dioxide atmosphere, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1h2a-2 with the yield of 62.1%.
The prepared spiro polymer material P1h2a-2 is characterized, and the infrared spectrum, nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum are similar to the results of example 7.
GPC measured the weight average molecular weight MW8500, MWD 2.98.
Example 14
The preparation method of the spiro polymer material described in this example has the following specific reaction formula:
wherein the monomer A is
Monomer B is
The preparation method of the spiro polymer material comprises the following steps:
(1) adding 370mg of monomer A, 408mg of monomer B and 12mL of toluene into a polymerization tube, reacting at 80 ℃ for 12 hours in a carbon dioxide atmosphere, stopping the reaction, and cooling to room temperature to obtain an intermediate product;
(2) dropwise adding the intermediate product into n-hexane under a stirring condition, precipitating a large amount of solid, stirring for 15min, performing suction filtration to obtain a solid, and drying the solid in a vacuum oven for 6h to obtain the spiro polymer material P1i2a-2 with the yield of 65.0%.
The prepared spiro polymer material P1i2a-2 is characterized, and the infrared spectrum, nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum are similar to the results of example 7.
GPC measured the weight average molecular weight MW37000, MWD 5.29.
Example 15
This example refers to the procedure of example 3, except that monomer B was used in an amount of 227mg, and the molar ratio of monomer A to monomer B was 1: 1.6. The spiro polymer material P1a2a-1(2) was prepared with a yield of 37.7%. GPC measured the weight average molecular weight MW6900 for MWD 1.81.
Example 16
This example refers to the procedure of example 3, with the only difference that 282mg of monomer B are used, and the molar ratio between monomer A and monomer B is 1: 2. Preparing the obtained spiro-polyCompound material P1a2a-1(3) at 70.4% yield. GPC measured the weight average molecular weight MW15200, MWD 2.41.
Example 17
This example refers to the procedure of example 3, except that 426mg of monomer B was used, and the molar ratio of monomer A to monomer B was 1: 3. The spiro polymer material P1a2a-1(4) is prepared, and the yield is 68.2%. GPC measured the weight average molecular weight MW13400, molecular weight distribution MWD 2.16.
Example 18
This example refers to the preparation of example 3, except that 24mL of toluene was used. The spiro polymer material P1a2a-1(5) is prepared with the yield of 54%. GPC measured the weight average molecular weight MW11900, MWD 2.38.
Example 19
This example refers to the preparation of example 3, except that 6mL of toluene was used. The spiro polymer material P1a2a-1(6) is prepared, and the yield is 76.5%. GPC measured the weight average molecular weight MW13400, molecular weight distribution MWD 2.53.
Example 20
This example refers to the preparation of example 3, except that 1, 2-dichloroethane is used instead of toluene as solvent. The spiro polymer material P1a2a-1(7) is prepared, and the yield is 62.6%. GPC measured the weight average molecular weight MW24000, MWD of 3.08.
Example 21
This example refers to the preparation of example 3, except that 1, 4-dioxane was used instead of toluene as solvent. The spiro polymer material P1a2a-1(8) is prepared, and the yield is 78.2%. GPC measured the weight average molecular weight MW12100, the molecular weight distribution is MWD 2.24.
Example 22
This example refers to the preparation of example 3, with the only difference that the reaction temperature is 25 ℃. The spiro polymer material P1a2a-1(9) is prepared with the yield of 24.3 percent. GPC measured the weight average molecular weight MW4400, MWD 1.69.
Example 23
This example refers to the preparation of example 3, with the only difference that the reaction temperature is 100 ℃. The spiro polymer material P1a2a-1(10) was prepared with a yield of 87.6%. GPC measured the weight average molecular weight MW11500, MWD 2.35.
Example 24
This example refers to the preparation of example 3, with the only difference that the reaction time is 1 h. The spiro polymer material P1a2a-1(11) was prepared with a yield of 14.6%. GPC measured the weight average molecular weight MW6100, MWD 1.69.
Example 25
This example refers to the preparation of example 3, with the only difference that the reaction time is 9 h. The spiro polymer material P1a2a-1(12) is prepared, and the yield is 72.0%. GPC measured the weight average molecular weight MW23900, MWD 3.23.
Example 26
This example refers to the preparation of example 3, with the only difference that the reaction time is 36 h. The spiro polymer material P1a2a-1(13) was prepared with a yield of 83.9%. GPC measured the weight average molecular weight MW18700, MWD 2.60.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (13)
1. A spiro polymer material is characterized in that the structural formula is as follows:
wherein R is1Selected from aliphatic or aromatic functional groups, R2Selected from aliphatic functional groups, n is an integer > 1;
the weight average molecular weight of the spiro polymer material is 4000-60000;
the preparation method of the spiro-polymer material comprises the following steps:
under the atmosphere of carbon dioxide, mixing and reacting the monomer A and the monomer B to obtain an intermediate product;
adding the intermediate product into a precipitator to obtain a precipitate, and filtering and collecting the precipitate to obtain the spiro polymer material;
wherein the structural formula of the monomer A is
The R is1Selected from aliphatic or aromatic functional groups; the structural formula of the monomer B is
The R is2Selected from aliphatic functional groups;
the R is1The structure of (a) includes any one of:
2. the spiro-polymeric material of claim 1, wherein R is said2Has the structure of-CxH2x+1(ii) a Wherein x is selected from an integer between 1 and 6.
3. Spirocyclic polymeric material according to claim 1, wherein the molar ratio of monomer A to monomer B is 1: 1.6-3.
4. A spiro-polymeric material according to claim 3, wherein the molar ratio of monomer A to monomer B is 1: 2-3.
5. A spiro-polymer material according to claim 1, wherein monomer A, monomer B and solvent are mixed and reacted under carbon dioxide atmosphere to obtain an intermediate product.
6. A spiro-polymeric material according to claim 5, wherein said solvent comprises one or more of toluene, 1, 2-dichloroethane, 1, 4-xylene and 1, 4-dioxane.
7. A spiro-polymeric material according to claim 6, wherein said solvent is toluene.
8. The spirocyclic polymeric material of claim 5, wherein said monomer A is present in the solvent at a concentration of 0.04-0.16 mol/L.
9. The spiro-polymeric material of claim 1, wherein the precipitating agent comprises one or both of n-hexane and petroleum ether.
10. The spiro-polymeric material of claim 9, wherein the precipitating agent is n-hexane.
11. A spiro-polymeric material according to claim 9, wherein the intermediate product is slowly added to the precipitant under stirring.
12. The spirocyclic polymeric material of claim 1, wherein said reaction temperature is 25-100 ℃ and said reaction time is 1-36 hours.
13. The spirocyclic polymeric material of claim 12, wherein said reaction temperature is 50-90 ℃ and said reaction time is 6-18 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810861656.0A CN108948349B (en) | 2018-08-01 | 2018-08-01 | Spiro-ring polymer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810861656.0A CN108948349B (en) | 2018-08-01 | 2018-08-01 | Spiro-ring polymer material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108948349A CN108948349A (en) | 2018-12-07 |
| CN108948349B true CN108948349B (en) | 2020-04-28 |
Family
ID=64466934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810861656.0A Expired - Fee Related CN108948349B (en) | 2018-08-01 | 2018-08-01 | Spiro-ring polymer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108948349B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836579A (en) * | 2019-03-07 | 2019-06-04 | 北京理工大学 | A kind of spiro polymer and its preparation method and application |
| CN111793009B (en) * | 2020-07-17 | 2022-06-28 | 河北工业大学 | Phthalonitrile monomer containing spiro structure and resin thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175600A (en) * | 1996-07-31 | 1998-03-11 | 三井东压化学株式会社 | Low-birefringent organic optical component and spirobiindan polymer |
| CN108047223A (en) * | 2017-12-21 | 2018-05-18 | 扬州大学 | Loop coil pyrido [2,1-a] isoquinoline compound and its synthetic method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3892795B2 (en) * | 2002-10-31 | 2007-03-14 | 株式会社東芝 | Polyimide optical material, polyimide precursor solution, and optical waveguide device |
-
2018
- 2018-08-01 CN CN201810861656.0A patent/CN108948349B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175600A (en) * | 1996-07-31 | 1998-03-11 | 三井东压化学株式会社 | Low-birefringent organic optical component and spirobiindan polymer |
| CN108047223A (en) * | 2017-12-21 | 2018-05-18 | 扬州大学 | Loop coil pyrido [2,1-a] isoquinoline compound and its synthetic method |
Non-Patent Citations (1)
| Title |
|---|
| Facile access to organotellurium heterocycles by nitration of bis (3, 5‐dimethylphenyl) ditelluride;Prabodhika R. Mallikarachy,et al.;《Journal of heterocyclic chemistry》;20090313;第42卷(第2期);第243-247页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108948349A (en) | 2018-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110003481B (en) | Preparation method of eight-arm hetero-arm star polymer | |
| CN110483773B (en) | Polyvinyl thioether ester and preparation method and application thereof | |
| CN108948349B (en) | Spiro-ring polymer material and preparation method thereof | |
| CN107325284B (en) | Hyperbranched polyphenyl triazole formate as well as preparation method and application thereof | |
| CN112574395A (en) | Conjugated microporous polymer based on 2,4, 6-tri (4-formylphenyl) pyrimidine and preparation method thereof | |
| CN112625220A (en) | Method for preparing protecting group-free same (different) type sugar-containing polymer by ROMP polymerization reaction | |
| JPS59130829A (en) | Manufacture of difunctional polyphenylene ethers | |
| Kavaklı et al. | Synthesis, characterization and amidoximation of a novel polymer: poly (N, N′-dipropionitrile acrylamide) | |
| CN112608472B (en) | Terminal functionalized polymer and method for carrying out CuAAC polymerization by utilizing copper acetylide | |
| CN107652443B (en) | Hyperbranched poly (ester-amine) with functional groups on surface and inside and preparation method thereof | |
| JP2691014B2 (en) | Porphyrin aluminum complex | |
| JP2850432B2 (en) | Copolymer and method for producing the same | |
| US11905378B2 (en) | High-grafting density cyclic comb shaped polymer and preparation method therefor | |
| CN111039879B (en) | Triazole compound/polymer containing sulfonyl and preparation method and application thereof | |
| CN112940162A (en) | Synthetic method of highly-ordered dendritic heterogeneous sugar-containing polymer containing multiple glycosyl groups | |
| CN115028834B (en) | Polyaryltriazole and preparation method and application thereof | |
| CN109384933B (en) | Silicon-containing aryne polymer and preparation method thereof | |
| CN113754881B (en) | Polyacetylenic amide compound and preparation method and application thereof | |
| CN112795005B (en) | Polycyclic linear polymer and preparation method thereof | |
| CN115093565B (en) | Polyphenyl sulfone ether triazole and preparation method and application thereof | |
| CN108976426B (en) | High-grafting-density ring comb polymer and preparation method thereof | |
| CN110540610B (en) | (methyl) acrylate polymer and preparation method thereof | |
| US20040030073A1 (en) | Optically active poly (N-methylbenzylmaleimide), method for its production and its use | |
| CN113461913B (en) | Polyethyleneimine analogue and synthesis method thereof | |
| CN108239278B (en) | Process for preparing amide-linked polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200428 Termination date: 20210801 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |