Three-component synthesis method of polyphosphonate

Abstract

The invention discloses a three-component synthesis method of polyphosphonate. The method comprises the following steps: 1, in an inert atmosphere, mixing RP (= O) OH2 type phosphonic acid, a monoepoxy compound and a Lewis acid-base pair catalyst, and carrying out polymerization reaction at 0-120 DEG C to obtain phosphonate functionalized polyether glycol; step 2, adding a third component into a reaction product obtained in the step 1, and carrying out stepwise polymerization reaction at 0-120 DEG C to obtain polyphosphonate; and the third component is at least one of polyisocyanate, a polyepoxy compound and carbonic ester. According to the method, commercialized phosphonic acid which is cheap and easy to obtain is used as a raw material, so far, the method is the simplest, convenient, efficient and atom-economical synthesis method of polyphosphonate; the side reactions such as phosphonate exchange and the like are completely inhibited by utilizing the high selectivity of Lewis acid-base to a catalytic system, and the generated polyphosphonate has abundant and controllable main chains, side groups and topological structures, so that the performance of the polymer can be accurately and flexibly regulated and controlled.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer synthesis, and in particular relates to a three-component synthesis method of polyphosphonate. Background Art

[0002] Phosphorus is a basic element that constitutes life. In particular, as a biological macromolecule that stores and transmits genetic information, the molecular skeleton of nucleic acid is constructed with phosphate as the connecting group of the structural unit. Therefore, polyphosphorus / phosphonate synthetic polymers have become extremely attractive biomimetic materials. Because phosphorus atoms have a high number of bonds and a variety of bonding methods, polyphosphorus / phosphonates have extremely rich structures and properties, and have shown comprehensive performance and application value that is different from or superior to conventional poly (carboxylic acid) esters in the fields of biomedicine, energy storage, coatings and adhesives. In addition, phosphorus-containing substances can form stable phosphates during the combustion process, thereby blocking the combustion chain reaction and improving the fire resistance level of the material. This is another unique advantage of polyphosphorus / phosphonates compared to most other polymer materials. Therefore, the development of polyphosphorus / phosphonate polymer materials is an important way to meet people's all-round pursuit of functionality, environmental protection, safety, etc.

[0003] At present, there are two main methods for the synthesis of polyphosphorus / phosphonates. 1) Step polymerization: small molecule diols and phosphorus / phosphonates are the main monomer types. The disadvantage is that most of them are condensation reactions, which are non-atom economical and have high energy consumption or pollution. 2) Chain ring-opening polymerization: five-membered ring phosphorus / phosphonates are the main monomers. The disadvantage is that the monomer preparation is complicated, and highly toxic and polluting raw materials and reagents (such as phosphorus chloride compounds) are required. They are also easy to hydrolyze and difficult to store, making them difficult to promote and apply on a large scale.

[0004] Phosphonic acid is a widely used precursor of phosphonate surfactants in industry. It has a large output and low price. Its preparation process does not require the use of phosphorus and chloride compounds, and has low environmental pollution. It is very suitable as a raw material for synthesizing polyphosphonates. However, the esterification reaction of phosphonic acid is not easy to carry out, and phosphonates have high chemical activity and are difficult to exist stably under conventional esterification conditions. The conditions usually used for the polycondensation reaction of dicarboxylic acids and diols (synthesizing polyesters) cannot be used for the reaction of phosphonic acid and diols (synthesizing polyphosphonates). Therefore, it is of great fundamental and practical significance to establish a new polymerization reaction to achieve efficient and highly selective conversion of phosphonic acid to polyphosphonates under mild conditions. Summary of the invention

[0005] In order to solve the shortcomings and deficiencies of the existing synthesis technology, the purpose of the present invention is to provide a RP (= O) OH 2 A three-component synthesis method for polyphosphonates using type phosphonic acid as raw materials.

[0006] The present invention uses RP(=O)OH 2The invention discloses a method for synthesizing polyphosphonates with phosphonic acid as a phosphorus source, which breaks through the limitations of the prior art in terms of simplicity, practicality, greenness, structural controllability and diversification. The method firstly obtains a phosphonate functionalized polyether diol by a chain ring-opening polymerization reaction between phosphonic acid and a monoepoxide in a Lewis acid-base catalytic system, and then gradually polymerizes the reaction with a third component (polyisocyanate, polyepoxide or carbonate). That is, a novel polyphosphonate is synthesized in a three-component reaction mode by connecting chain (ring-opening) polymerization and gradual polymerization in series. Phosphonic acid has a large output, low price and diverse structure. The preparation process does not require the use of phosphorus-chlorine compounds. The second and third components are also widely available, cheap and easy to obtain. The method also does not involve halogen in the formation process of polyphosphonates, and no or only a small amount of small molecule byproducts are generated. Compared with the existing polyphosphonate synthesis method, the method proposed in the present invention has the characteristics of high chemical selectivity, cheap raw materials, easy availability, easy storage, high commercialization and diverse structures, avoiding the use of highly toxic substances, environmentally friendly, mild reaction conditions, easy operation, and rich main chain, side group and topological structure of the product, which are easy to regulate. In addition, the method can flexibly regulate the main chain, side group and topological structure, greatly expanding the structure and performance of polyphosphonate.

[0007] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0008] A three-component synthesis method of polyphosphonate, which synthesizes polyphosphonate in a three-component manner by connecting chain (ring-opening) polymerization and stepwise polymerization, comprises the following steps:

[0009] In the first step, in an inert atmosphere, RP(=O)OH 2 A type phosphonic acid, a monoepoxide and a Lewis acid-base catalyst are mixed and polymerized at 0 to 120° C. to obtain a phosphonate functionalized polyether diol;

[0010] In the second step, a third component is added to the reaction product of the first step, and a stepwise polymerization reaction is carried out at 0 to 120° C. to obtain a polyphosphonate; the third component is at least one of a polyisocyanate, a polyepoxide, and a carbonate.

[0011] Furthermore, the RP(=O)OH 2The phosphonic acids include, but are not limited to, (1) alkylphosphonic acids having 1 to 18 carbon atoms, (2) phenylphosphonic acid, (3) benzylphosphonic acid, (4) vinylphosphonic acid, (5) perfluoroalkylphosphonic acid having 2 to 17 carbon atoms, (6) cinnamylphosphonic acid, (7) (pyridin-3-ylmethyl)phosphonic acid, (8) (pyridin-2-ylmethyl)phosphonic acid, (9) 12-azidododecylphosphonic acid, (10) 2,3,4,5,6-pentaphosphonic acid, Fluorobenzylphosphonic acid, (11) 4-phenylbutylphosphonic acid, (12) 2-bicyclo[2.2.1]heptylphosphonic acid, (13) 3-aminopropane-1-phosphonic acid, (14) Cbz-3-aminopropane-1-phosphonic acid, (15) 3-chlorophenylphosphonic acid, (16) 4-methoxyphenylphosphonic acid and (17) a mixture of one or two of the following: the ratio of the two phosphonic acids in the mixture is 1:(1-100). The specific structural formula is as follows:

[0012]

[0013] Further, the monoepoxy compound mainly refers to a compound having one epoxy group, and the number of carbon atoms of the monoepoxy compound is 2-10;

[0014] More preferably, the monoepoxide is selected from (1) ethylene oxide, (2) propylene oxide, (3) butylene oxide, or a mixture of two of them; the ratio of the two monoepoxides in the mixture is 1:(1-100). The specific structural formula is as follows:

[0015]

[0016] Furthermore, the polyisocyanate includes, but is not limited to, (1) 1,4-tetramethylene diisocyanate, (2) 1,6-hexamethylene diisocyanate, (3) 1,4-diisocyanate cyclohexane, (4) 4,4'-dicyclohexylmethane diisocyanate, (5) isophorone diisocyanate, (6) m-phenylene diisocyanate, (7) p-phenylene diisocyanate, (8) 2,4-toluene diisocyanate, (9) 2,6-toluene diisocyanate, (10) 1-methoxyphenyl-2,4-diisocyanate, (11) tetramethylmethylene diisocyanate, (12) 1,5-naphthalene diisocyanate ester, (13) 2,2'-diphenylmethane diisocyanate, (14) 2,4'-diphenylmethane diisocyanate, (15) 4,4'-diphenylmethane diisocyanate, (16) 4,4'-biphenylene diisocyanate, (17) 3,3'-dimethoxy-4'-,4'-biphenylene diisocyanate, (18) 2,4,6-triisocyanate toluene, (19) 4,4',4"-triphenylmethane triisocyanate and (20) a mixture of one or two of hexamethylene diisocyanate trimer; the ratio of the two isocyanates in the mixture is 1:(1-100). The specific structural formula is as follows:

[0017]

[0018] Further, the polycyclic epoxy compound is at least one of a binary epoxy compound and a ternary epoxy compound;

[0019] Furthermore, the polycyclic epoxy compound includes, but is not limited to, (1) a linear alkyl terminal dioxirane having an alkyl carbon number of 1 to 20, (2) ethylene glycol diglycidyl ether or an alkyl glycol diglycidyl ether having a carbon number of 3 to 20, (3) polyethylene glycol diglycidyl ether, (4) neopentyl glycol diglycidyl ether, (5) 1,2-cyclohexanediol diglycidyl ether, (6) resorcinol diglycidyl ether, (7) a linear alkyl terminal diglycidyl dicarboxylate having an alkyl carbon number of 0 to 20, (8) ) 1,2-cyclohexanedicarboxylic acid diglycidyl ester, (9) 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, (10) hydantoin epoxy resin, (11) bisphenol A propoxy acid diglycidyl ether, (12) bisphenol A diglycidyl ether, (13) 1,3-bis(3-glycidyl ether propyl)tetramethyldisiloxane and (14) a mixture of one or two of the following; the ratio of the two epoxy compounds in the mixture is 1:(1-100). The specific structural formula is as follows:

[0020]

[0021] Furthermore, the carbonate includes, but is not limited to, a mixture of one or two of (1) dialkyl carbonates having 1 to 18 carbon atoms, (2) dicyclohexyl carbonate, (3) diphenyl carbonate, (4) methyl trifluoroethyl carbonate, (5) ethyl trifluoroethyl carbonate, (6) methyl ethyl ether trifluoroethyl carbonate, and (7) bis trifluoroethyl carbonate; the ratio of the two carbonates in the mixture is 1:(1 to 100). The specific structural formula is as follows:

[0022]

[0023] Furthermore, the RP(=O)OH 2 The molar ratio of the phosphonic acid to the monoepoxide is 1:(2-200);

[0024] Furthermore, the molar ratio of the active functional groups in the third component to the alcoholic hydroxyl groups in the phosphonate functionalized polyether diol is 1:(1-1.2); the active functional groups include isocyanate groups, epoxy groups and carbonate groups.

[0025] Furthermore, the Lewis acid-base catalyst is composed of an organic base and an alkyl boron; the molar ratio of the active functional group, the organic base and the alkyl boron in the third component is 1:(0.005-2):(0.005-5); the active functional group includes an isocyanate group, an epoxy group and a carbonate group.

[0026] Further preferably, the organic base includes but is not limited to various tertiary amines (DABCO, PMDETA, ME 6 TREN, sparteine), amidines (DBN, DBU), guanidines (TBD, MTBD, TMG, PMG), triaminophosphine (HMTP, HETP, TMAP, TIPAP) and phosphazene bases (BEMP, t BnP 1 , t BnP 2 ,EtP 2 , t BnP 4 ), lithium / sodium / potassium / cesium tert-butoxide, lithium / sodium / potassium / cesium pivalate, ionic compounds (thiourea-containing ionic compounds, urea-containing ionic compounds, carbamate-containing ionic compounds, R 1 , R 2 , R 3 R is independently selected from H, phenyl, tolyl, benzyl, a cycloalkyl group having 3 to 8 carbon atoms, a chain alkyl group having 1 to 20 carbon atoms, and a chain alkyl group having 1 to 8 carbon atoms of a borane substituent; 4 ~R 11Each of them is independently selected from an alkyl group with 1 to 8 carbon atoms and a benzyl group; Z is selected from at least one of N and P. The specific structural formula is as follows:

[0027]

[0028] Further preferably, the alkyl boron includes but is not limited to B-isopinocampheyl-9-borabicyclo[3.3.1]nonane (S-Alphine-Borane), tri-sec-butylborane (T s BuB), triisopropylborane (T i At least one of PrB), trimethylborane (TMB), other tri(straight-chain) alkylboranes (TAB; carbon chain length ranges from 2 to 8), diethylmethoxyborane (MOEB) and trimethyl borate (TMBO). The specific structural formula is as follows:

[0029]

[0030] Furthermore, the polymerization reaction is carried out in bulk or in an organic solvent, and the organic solvent is a mixture of one or more of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, n-hexane, cyclohexane, acetone, ethyl acetate and tert-butanol; the initial concentration of the monoepoxide is 5 to 20 mol / L.

[0031] More preferably, when the organic solvent is a mixture of two solvents, the volume ratio of the two solvents is 1:(1-100).

[0032] Furthermore, the temperature of the first step polymerization reaction is 20-60°C, and the time of the first step polymerization reaction is 0.5-48h; the temperature of the second step step polymerization reaction is 20-60°C, and the time of the second step step polymerization reaction is 1-120h.

[0033] Furthermore, the reactants of the second step of stepwise polymerization can be only phosphonate functionalized polyether diol and a binary third component to obtain a linear polyphosphonate; or a certain amount of a ternary third component (a trivalent isocyanate or a trivalent epoxy compound) can be added to obtain a branched or cross-linked polyphosphonate. The molar ratio of the binary to ternary third components is 1:(0.01-1).

[0034] Furthermore, the two-step reaction can be carried out continuously in the same reactor without the need to separate and purify the intermediate product phosphonate functionalized polyether diol. Alternatively, the phosphonate functionalized polyether diol can be separated and purified before the second step polymerization reaction.

[0035] Further preferably, the phosphonate functionalized polyether diol is separated and purified before the second step of stepwise polymerization reaction, which requires the addition of a Lewis acid-base catalyst (organic base and alkyl boron) to carry out the stepwise polymerization reaction in bulk or in an organic solvent.

[0036] In the synthesis method of the present invention, the synergistic catalytic effect of the Lewis acid-base pair and the unique chemical selectivity completely inhibit the phosphonate exchange and other destructive chain transfer reactions to monomers or polymers, and the third component and the phosphonate functionalized polyether diol can be efficiently and selectively step-wise polymerized at room temperature, and the generated polyphosphonate has a rich and controllable main chain, side group and topological structure. When the third component is a polyisocyanate, a polyphosphonate-polyurethane (phosphonate-carbamate bifunctional polymer) can be obtained; when the third component is a polyepoxide, a polyhydroxy polyphosphonate (phosphonate-hydroxy bifunctional polymer) can be obtained; when the third component is a carbonate, a polyphosphonate-polycarbonate (phosphonate-carbonate bifunctional polymer) can be obtained.

[0037] In summary, the present invention has created a three-component synthesis method for polyphosphonate that connects chain (ring-opening) polymerization and step-by-step polymerization in series, which has significant simplicity, economy, practicality and environmental friendliness. The monomer raw materials are widely available, cheap and easy to obtain, and have diverse structures, and rich and easily adjustable new polymer structures and properties can be obtained.

[0038] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0039] (1) The present invention establishes RP(=O)OH for the first time 2 The invention relates to a method for the chemoselective ethoxylation of phosphonic acid and monoepoxide (chemoselective chain ring-opening polymerization of epoxide initiated by phosphonic acid) to achieve a controlled hydroxylation reaction of phosphonic acid to diol. Compared with the existing phosphonic acid esterification method, it has significantly improved efficiency, selectivity and atom economy, and the reaction conditions are mild and environmentally friendly.

[0040] (2) Using the obtained phosphonate functionalized polyether and the third component as raw materials, in the same or similar Lewis acid-base catalytic system, relying on the two-component synergistic catalytic mechanism, a variety of chemically selective step-by-step polymerization reactions are established to achieve a series of new polyphosphonates (in series) controllable synthesis. Compared with the existing polyphosphonate synthesis methods, this method does not require the preparation of complex (cyclic) phosphorus-containing monomers. The raw materials used are all highly commercialized, cheap and easily available compounds with a wide variety and rich structures. The flexibility of the three-component reaction can be fully utilized. By changing the substituents of the phosphonic acid, the type and amount of the epoxy compound, the type and proportion of the third component, etc., the main chain, side group and topological structure of the polymer can be flexibly and accurately regulated. Therefore, the simplicity, practicality, and richness of polymer structure and performance are greatly improved compared with the existing methods.

[0041] (3) The present invention avoids the use of highly toxic phosphorus-containing raw materials (such as phosphorus chloride compounds), and the reaction conditions for generating polyphosphonates are relatively mild, generally without the need for high temperature and strong acid / strong alkaline reaction conditions. The reaction can be carried out using a small amount of catalyst with a simple structure, and no or only a small amount of small molecule by-products are generated. Therefore, compared with existing polyphosphonate synthesis methods, the present invention has significantly improved (atomic) economy, practicality and environmental friendliness.

[0042] (4) Existing polyphosphorus / phosphonate materials lack side functional groups that can be used for post-modification. The present invention can introduce reactive side functional groups such as vinyl and hydroxyl groups into the polyphosphonate structure by using phosphonic acid containing functional groups or using polycyclic epoxy compounds as the third component, so that the polyphosphonate can be modified; through functional group conversion, graft polymerization, coupling reaction, etc., the structure and performance of the polyphosphonate can be evolved, further broadening the functions and application scope of polyphosphonate materials.

[0043] (5) Both steps of the reaction of the present invention do not require the use of heavy metal catalysts and can be efficiently carried out under the action of organic or alkali metal catalysts, further improving the environmental friendliness of the synthesis method and the applicability of the obtained polyphosphonate materials in the fields of energy, microelectronics, biomedicine, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1a The stepwise polymerization product (polyphosphonate) of octadecylphosphonic acid, ethylene oxide and 1,4-butanediol diglycidyl ether in Example 1 1 H NMR spectra.

[0045] Figure 1b SEC chart of the stepwise polymerization product (polyphosphonate) of octadecylphosphonic acid, ethylene oxide and 1,4-butanediol diglycidyl ether in Example 1.

[0046] Figure 2aThe stepwise polymerization product (polyphosphonate) of hexylphosphonic acid, ethylene oxide and 1,4-butanediol diglycidyl ether in Example 5 1 H NMR spectra.

[0047] Figure 2b SEC chart of the stepwise polymerization product (polyphosphonate) of hexylphosphonic acid, ethylene oxide and 1,4-butanediol diglycidyl ether in Example 5.

[0048] Figure 3a is the stepwise polymerization product (polyphosphonate) of octadecylphosphonic acid, ethylene oxide and 1,6-hexamethylene diisocyanate in Example 17 1 H NMR spectra.

[0049] Figure 3b SEC chart of the stepwise polymerization product (polyphosphonate) of octadecylphosphonic acid, ethylene oxide and 1,6-hexamethylene diisocyanate in Example 17. DETAILED DESCRIPTION

[0050] The specific implementation modes of the present invention are described in detail below in conjunction with examples, but the implementation modes of the present invention are not limited thereto.

[0051] The reaction degree of the active groups in the third component and the structural characteristics of the resulting polymers in the following examples were measured by a Bruker AV400 liquid nuclear magnetic resonance spectrometer ( 1 H NMR) was measured, and the solvent was deuterated dimethyl sulfoxide. The molecular weight and dispersity of the obtained polymer were measured by size exclusion chromatography (SEC), and the instrument used an Agilent 1260infinity II pump and a PLgel 5μm mixed-C chromatographic column, with N,N-dimethylformamide (DMF) as the mobile phase, a column temperature of 50°C, and a flow rate of 1mL / min; a series of polymethyl methacrylate standard samples were used as calibration curves. The parts used in the following examples are all molar parts. As an example, the molar parts can be mol, mmol, etc., or any other amount commonly used in the art.

[0052] Example 1

[0053] In this embodiment, an anionic polymerization reaction is carried out with octadecylphosphonic acid (ODPA) as an initiator and ethylene oxide (EO) as a monomer under the condition of a Lewis acid-base pair as a catalyst to generate an octadecylphosphonate functionalized polyether diol; and 1,4-butanediol diglycidyl ether (BDGE) and the above reaction product are further gradually polymerized in a solution at room temperature to prepare a polyphosphonate based on ODPA, EO and BDGE by a one-pot method. The specific operation is as follows:

[0054] Under nitrogen atmosphere, 1.06 parts (4.29 mmol) of ODPA, 2.40 mL of tetrahydrofuran, 0.15 parts (0.60 mmol) of triethylborane and 0.05 parts (0.20 mmol) of phosphazene base were added. t BnP 1 Add the dried glass reactor in sequence and stir and mix thoroughly. Connect the glass reactor to the vacuum line, remove some of the gas in the bottle, and cool it with an ice water bath. Distill 14.84 parts (60.0mmol) of dried EO at -20°C. After reacting at room temperature for 10 hours, the solution becomes noticeably viscous. After the reaction is completed, continue to add 1 part (4.05mmol) of BDGE to the reaction bottle under nitrogen. Stir and mix evenly, seal the glass reactor and react at room temperature for 7 hours. After the reaction is completed, add methanol to terminate the reaction. In the first 1 hour, the change in solution viscosity is not much different; after reacting for 3 hours, the solution viscosity increases significantly in a few hours, which conforms to the characteristics of linear step-by-step polymerization, that is, the reaction degree of the group is high in the early stage of the reaction, but the molecular weight does not change significantly; in the later stage of the reaction, the reaction degree of the group changes slightly but the molecular weight changes significantly. In this embodiment, the molar ratio of BDGE, ODPA, EO, organic base and alkyl boron is 1:1.06:14.84:0.05:0.15. After the polymerization is completed, ether is added for reverse precipitation three to four times to remove the catalyst, and the obtained product is a colorless transparent viscous liquid. The precipitate is collected and vacuum dried to obtain polyphosphonate.

[0055] Polyphosphonates obtained by stepwise polymerization of ODPA, EO and BDGE 1 The results of H NMR and SEC tests are shown in Figure 1a , Figure 1b The purified product 1 The H NMR spectrum fully shows that the polymer is a linear polymer. In addition, 1 In H NMR, no characteristic signal peaks (i.e., ether bonds formed by secondary alcoholic hydroxyl groups) that may be formed by the continued participation of the secondary alcoholic hydroxyl groups in the ring-opening reaction of the epoxy groups were observed. This indicates that under this catalytic system, the difference in the reactivity of the primary alcoholic hydroxyl groups and the secondary alcoholic hydroxyl groups is amplified, so that the primary alcoholic hydroxyl groups react with the epoxy groups preferentially over the secondary alcoholic hydroxyl groups, and the latter have no chance to participate in the reaction when the former exists, so the secondary alcoholic hydroxyl groups of the side groups are completely retained, which can ensure that the product structure has a high degree of uniformity. 1 H NMR showed that the reaction degree (conversion rate) of the epoxy groups was greater than 99%. The molecular weight of the obtained polyphosphonate was 57.8 kg / mol as measured by SEC, and the dispersity was 2.34.

[0056] The structure of polyphosphonate is shown below:

[0057]

[0058] Example 2

[0059] In this example, the ratio of ODPA to EO was adjusted, 1.06 parts (1.2 mmol) of ODPA and 53 parts (60 mmol) of EO were added, and the rest was the same as in Example 1. The first step reaction was shortened to 5 h at room temperature, and the second step reaction was extended to 12 h. 1 H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of BDGE, ODPA, EO, organic base and alkyl boron is 1:1.06:53:0.05:0.15. The molecular weight of the obtained polyphosphonate is 89.2 kg / mol measured by SEC, and the dispersity is 1.85.

[0060] Example 3

[0061] In this example, the Lewis acid-base ratio was changed by adding 0.01 parts (0.011 mmol) of phosphazene base t BnP 1 and 0.03 parts (0.034 mmol) of triethylborane, the rest was the same as in Example 1, the first step reaction time was 15 h at room temperature, the second step reaction time was 20 h, 1 H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of BDGE, ODPA, EO, organic base and alkyl boron is 1:1.06:14.84:0.01:0.03. The molecular weight of the obtained polyphosphonate is 43.5 kg / mol measured by SEC, and the dispersity is 2.33.

[0062] Example 4

[0063] In this example, the phosphonic acid structure is changed, ODPA is replaced by dodecylphosphonic acid, and the rest is the same as in Example 1. The first step reaction time at room temperature is 10 hours, and the second step reaction time is 6 hours. 1 H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of BDGE, dodecylphosphonic acid, EO, organic base and alkyl boron is 1:1.06:14.84:0.05:0.15. The molecular weight of the obtained polyphosphonate is 83.2 kg / mol measured by SEC, and the dispersity is 2.33.

[0064] The structure of polyphosphonate is shown below:

[0065]

[0066] Example 5

[0067] In this example, the phosphonic acid structure is changed, ODPA is replaced by hexylphosphonic acid, and the rest is the same as in Example 1. The first step reaction time at room temperature is 8 hours, and the second step reaction time is 6 hours. 1 H NMR shows that the reaction degree of epoxy groups can reach more than 99%. In this embodiment, the molar ratio of BDGE, hexylphosphonic acid, EO, organic base and alkyl boron is 1:1.06:14.84:0.05:0.15. The obtained polyphosphonate purified product 1 H NMR and SEC images are shown in Figure 2a and Figure 2b The molecular weight of the obtained polyphosphonate was measured by SEC to be 47.7 kg / mol, and the dispersion degree was 2.13.

[0068] The structure of polyphosphonate is shown below:

[0069]

[0070] Example 6

[0071] In this example, the phosphonic acid structure is changed, ODPA is replaced by phenylphosphonic acid, and the rest is the same as in Example 1. The first step reaction time at room temperature is 5 hours, and the second step reaction time is 6 hours. 1 H NMR shows that the reaction degree of the epoxy group can reach more than 99%. In this embodiment, the molar ratio of BDGE, phenylphosphonic acid, EO, organic base and alkyl boron is 1:1.06:14.84:0.05:0.15. The molecular weight of the obtained polyphosphonate is 49.4 kg / mol measured by SEC, and the dispersity is 2.12.

[0072] The structure of polyphosphonate is shown below:

[0073]

[0074] Example 7

[0075] In this example, the tetrahydrofuran solvent in Example 1 was replaced with toluene solvent, and the rest was the same as in Example 1. The first step reaction time at room temperature was 11 hours, the second step reaction time was 8 hours, and the crude product 1 H NMR showed that the reaction degree of the epoxy groups could reach more than 99%. The molecular weight of the obtained polyphosphonate was 45.3 kg / mol and the dispersity was 1.88 as measured by SEC.

[0076] Example 8

[0077] In this example, the tetrahydrofuran solvent in Example 1 was replaced with tert-butyl alcohol solvent, and the rest was the same as Example 1. The first step reaction time at room temperature was 10 hours, the second step reaction time was 6 hours, and the crude product 1The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyphosphonate was 46.5 kg / mol and the dispersion was 1.97 as measured by SEC.

[0078] Example 9

[0079] In this example, the first step of the reaction in Example 1 was carried out at room temperature for 10 hours, and the second step was carried out at 50°C with a reaction time shortened to 3 hours. The rest was the same as in Example 1. 1 The reaction degree of epoxy groups measured by HNMR was more than 99%. The molecular weight of the obtained polyphosphonate was 77.9 kg / mol and the dispersion was 2.53 as measured by SEC.

[0080] Example 10

[0081] In this example, the phosphazene base in Example 1 t BnP 1 The reaction time of the first step was 18 hours, and the reaction time of the second step was 15 hours. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyphosphonate was 51.2 kg / mol and the dispersion was 3.02 as measured by SEC.

[0082] Embodiment 11

[0083] In this example, the phosphazene base in Example 1 t BnP 1 The reaction time of the first step was 16 h, and the reaction time of the second step was 13 h. 1 The reaction degree of epoxy groups measured by H NMR was more than 99%. The molecular weight of the obtained polyphosphonate was 48.6 kg / mol and the dispersion was 2.77 as measured by SEC.

[0084] Example 12

[0085] In this example, BDGE in Example 1 is replaced with bisphenol A diglycidyl ether, and the rest is the same as Example 1. The first step reaction time at room temperature is 10 hours, and the second step reaction time is 5 hours. 1 H NMR showed that the reaction degree (conversion rate) of the epoxy groups was greater than 99%. The molecular weight of the obtained polyphosphonate was 51.4 kg / mol as measured by SEC, and the dispersity was 2.33.

[0086] The structure of polyphosphonate is shown below:

[0087]

[0088] Embodiment 13

[0089] In this example, BDGE in Example 1 is replaced with 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane, and the rest is the same as Example 1. The first step reaction time at room temperature is 8 hours, and the second step reaction time is 7 hours. 1 H NMR showed that the reaction degree (conversion rate) of the epoxy groups was greater than 99%. The molecular weight of the obtained polyphosphonate was 61.2 kg / mol as measured by SEC, and the dispersity was 2.27.

[0090] Due to the large bond angle, high bond energy and partial ionic bond properties of the silicon-oxygen bond, polysiloxane has excellent properties different from carbon chain polymers, making silicone products widely used in aerospace, national defense, automobiles, construction, textiles, medical and other fields. Introducing silicon-oxygen bonds from 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane monomers to the polyphosphonate main chain can give the polyphosphonate material properties such as high air permeability, low surface energy, high and low temperature resistance, corrosion resistance, and low dielectric properties.

[0091] The structure of polyphosphonate is shown below:

[0092]

[0093] Embodiment 14

[0094] In this example, BDGE in Example 6 was replaced with hydantoin epoxy resin, and the rest was the same as Example 6. The first step reaction time at room temperature was 8 hours, and the second step reaction time was 7 hours. 1 H NMR showed that the reaction degree (conversion rate) of the epoxy groups was greater than 99%. The molecular weight of the obtained polyphosphonate was 60.5 kg / mol as measured by SEC, and the dispersity was 2.33.

[0095] The structure of polyphosphonate is shown below:

[0096]

[0097] Embodiment 15

[0098] In this example, BDGE in Example 6 was replaced with resorcinol diglycidyl ether, and the rest was the same as Example 6. The first step reaction time at room temperature was 8 hours, and the second step reaction time was 4 hours. 1 H NMR showed that the reaction degree (conversion rate) of the epoxy groups was greater than 99%. The molecular weight of the obtained polyphosphonate was 75.2 kg / mol as measured by SEC, and the dispersity was 2.35.

[0099] The structure of polyphosphonate is shown below:

[0100]

[0101] Example 16

[0102] In this example, the monomer structure is changed, BDGE is replaced with a mixture of BDGE and 1,3,5-triglycidyl-S-triazinetrione (molar ratio of 0.7:0.2), and a cross-linked polyphosphonate is prepared by a one-pot method. The specific operation is as follows:

[0103] Under nitrogen atmosphere, 1.06 parts (4.29 mmol) of ODPA, 2.40 mL of tetrahydrofuran, 0.15 parts (0.60 mmol) of triethylborane and 0.05 parts (0.20 mmol) of phosphazene base were added. t BnP 1 Add the dried glass reactor in sequence and stir and mix thoroughly, connect the glass reactor to the vacuum line, remove some of the gas in the bottle, and cool it with an ice water bath. Steam 14.84 parts (60.0mmol) of dried EO at -20°C. After reacting for 5h at room temperature, the solution becomes noticeably sticky. After the reaction is completed, continue to add 0.7 parts (2.84mmol) of BDGE to the reaction bottle under nitrogen. Stir and mix evenly, seal the glass reactor and react at room temperature for 6h, then add 0.2 parts (0.81mmol) of 1,3,5-triglycidyl-S-triazinetrione, seal the glass reactor and react at room temperature for 1h, then pour it into the mold to shape, and obtain a cross-linked polyphosphonate. In this embodiment, the molar ratio of BDGE, 1,3,5-triglycidyl-S-triazinetrione, ODPA, EO, organic base and alkyl boron is 0.7:0.2:1.06:14.84:0.05:0.15. The product obtained was a colorless gummy solid.

[0104] Embodiment 17

[0105] In this embodiment, an anionic polymerization reaction is carried out with ODPA as an initiator and EO as a monomer under the condition of a Lewis acid-base pair as a catalyst to generate an octadecylphosphonate functionalized polyether diol; and further, 1,6-hexamethylene diisocyanate (HDI) and the above reaction product are gradually polymerized in a solution at room temperature to prepare a polyphosphonate-based polyurethane based on ODPA, EO and HDI in one pot. The specific operation is as follows:

[0106] Under nitrogen atmosphere, 1 part (4.29mmol) of ODPA, 3.0mL of tetrahydrofuran, 0.15 parts (0.64mmol) of triethylborane and 0.05 parts (0.22mmol) of organic base 1,8-diazabicyclo[5.4.0]undec-7-ene were added to the dried glass reactor in sequence and stirred and mixed thoroughly. The glass reactor was connected to the vacuum line, some of the gas in the bottle was removed, and the temperature was cooled with an ice water bath. 14 parts (60.0mmol) of dried EO were distilled in at -20°C. After reacting at room temperature for 6h, the solution became obviously viscous. After the reaction was completed, 1 part (4.29mmol) of HDI was continued to be added to the reaction bottle under nitrogen conditions. Stir and mix evenly, seal the glass reactor and react at room temperature for 12h, and add acetic acid to terminate the reaction after the reaction is completed. In this embodiment, the molar ratio of HDI, ODPA, EO, organic base and alkyl boron is 1:1:14:0.05:0.15. After the polymerization is completed, n-hexane is added for reverse precipitation three to four times to remove the catalyst. The resulting product is a colorless, transparent viscous liquid. The precipitate is collected and vacuum dried to obtain the obtained polyphosphonate-based polyurethane purified product. 1 H NMR and SEC images are shown in Figure 3a and Figure 3b The molecular weight of the obtained polyphosphonate-based polyurethane was measured by SEC to be 35.2 kg / mol, and the dispersion degree was 2.95.

[0107]

[0108] Embodiment 18

[0109] In this example, EO in Example 17 was replaced with propylene oxide, and the rest was the same as Example 17. The first step reaction time at room temperature was 8 hours, and the second step reaction time was 8 hours. After the polymerization was completed, methanol was added for reverse precipitation three to four times to remove the catalyst, and the obtained product was a colorless transparent viscous liquid. The molecular weight of the obtained polyphosphonate-based polyurethane was measured by SEC to be 40.5 kg / mol, and the dispersity was 2.42.

[0110] The structure of polyphosphonate-based polyurethane is shown below:

[0111]

[0112] Embodiment 19

[0113] In this example, HDI in Example 18 was replaced with isophorone diisocyanate, and the rest was the same as Example 18. The first step reaction time at room temperature was 8 hours, and the second step reaction time was 7 hours. The molecular weight of the obtained polyphosphonate-based polyurethane was measured by SEC to be 62.2 kg / mol, and the dispersity was 2.25.

[0114] The structure of polyphosphonate-based polyurethane is shown below:

[0115]

[0116] Embodiment 20

[0117] In this example, HDI in Example 18 was replaced with 4,4'-diphenylmethane diisocyanate, and the rest was the same as Example 18. The first step reaction time at room temperature was 8 hours, and the second step reaction time was 2 hours. The molecular weight of the obtained polyphosphonate-based polyurethane was measured by SEC to be 80.5 kg / mol, and the dispersity was 3.02.

[0118] The structure of polyphosphonate-based polyurethane is shown below:

[0119]

[0120] Embodiment 21

[0121] In this example, the isophorone diisocyanate in Example 19 is replaced with isophorone diisocyanate and hexamethylene diisocyanate trimer. Under the same conditions as in Example 19, an octadecylphosphonate functionalized polyether is obtained. First, 0.7 parts of isophorone diisocyanate is added to the mixture for reaction for 4 hours, and then 0.2 parts of hexamethylene diisocyanate trimer is added to the mixture and stirred for 10 minutes, and then poured into a mold for shaping. The obtained polyphosphonate is a cross-linked polyurethane.

[0122] Embodiment 22

[0123] In this example, the isophorone diisocyanate in Example 19 is replaced by hexamethylene diisocyanate trimer, and the amount used is 0.67 parts, and the rest is the same as in Example 19. The second step is to react at room temperature for 2 hours, and the obtained polyphosphonate is a cross-linked polyurethane.

[0124] Embodiment 23

[0125] In this example, ODPA in Example 18 was replaced with phenylphosphonic acid, and the rest was the same as Example 18. The first step reaction time at room temperature was 6 hours, and the second step reaction time was 8 hours. The molecular weight of the obtained polyphosphonate-based polyurethane was measured by SEC to be 35.5 kg / mol, and the dispersity was 2.64.

[0126] The structure of polyphosphonate-based polyurethane is shown below:

[0127]

[0128] Embodiment 24

[0129] In this example, HDI in Example 17 was replaced with diphenyl carbonate, and the rest was the same as Example 17. The first step reaction time at room temperature was 8 hours, and the second step reaction time was 10 hours. The molecular weight of the obtained polyphosphonate was measured by SEC to be 34.7 kg / mol, and the dispersity was 2.46.

[0130] The structure of polyphosphonate is shown below:

[0131]

[0132] Embodiment 25

[0133] In this example, HDI in Example 17 was replaced with bistrifluoroethyl carbonate, and the rest was the same as Example 17. The first step reaction time at room temperature was 8 hours, and the second step reaction time was 6 hours. The molecular weight of the obtained polyphosphonate was measured by SEC to be 38.2 kg / mol, and the dispersity was 2.51.

[0134] The structure of polyphosphonate is shown below:

[0135]

[0136] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A three-component synthesis method of polyphosphonate, characterized in that: The steps include: The first step is to mix RP(=O)OH2 type phosphonic acid, a monoepoxide and a Lewis acid-base catalyst in an inert atmosphere and polymerize them at 0-120° C. to obtain a phosphonate functionalized polyether diol; In the second step, a third component is added to the reaction product of the first step, and a stepwise polymerization reaction is carried out at 0 to 120° C. to obtain a polyphosphonate; the third component is at least one of a polyisocyanate, a polyepoxide, and a carbonate.

2. The three-component synthesis method of polyphosphonate according to claim 1, characterized in that: The RP(=O)OH2 type phosphonic acid is selected from one or a mixture of two of alkylphosphonic acid having 1 to 18 carbon atoms, phenylphosphonic acid, benzylphosphonic acid, vinylphosphonic acid, perfluoroalkylphosphonic acid having 2 to 17 carbon atoms, cinnamyl phosphoric acid, (pyridin-3-ylmethyl)phosphonic acid, (pyridin-2-ylmethyl)phosphonic acid, 12-azidododecylphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, 4-phenylbutylphosphonic acid, 2-bicyclo[2.2.1]heptylphosphonic acid, 3-aminopropane-1-phosphonic acid, Cbz-3-aminopropane-1-phosphonic acid, 3-chlorophenylphosphonic acid, 4-methoxyphenylphosphonic acid and p-carboxyphenylphosphonic acid.

3. The three-component synthesis method of polyphosphonate according to claim 1, characterized in that: The polycyclic epoxy compound is at least one of a binary epoxy compound and a ternary epoxy compound; The monoepoxy compound has 2-10 carbon atoms.

4. The three-component synthesis method of polyphosphonate according to claim 3, characterized in that: The monoepoxy compound is selected from one or a mixture of two of ethylene oxide, propylene oxide and butylene oxide.

5. The three-component synthesis method of polyphosphonate according to claim 1, characterized in that: The polyisocyanate is selected from 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-diisocyanate cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, tetramethyl m-xylylene diisocyanate, A mixture of one or two of 1,5-naphthalene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4'-,4'-biphenylene diisocyanate, 2,4,6-triisocyanate toluene, 4,4',4"-triphenylmethane triisocyanate and hexamethylene diisocyanate trimer; The polycyclic epoxy compound is selected from one or a mixture of two of the following: linear alkyl terminal dioxirane with an alkyl carbon number of 1 to 20, ethylene glycol diglycidyl ether, alkyl glycol diglycidyl ether with a carbon number of 3 to 20, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, resorcinol diglycidyl ether, linear alkyl terminal dicarboxylic acid diglycidyl ester with an alkyl carbon number of 0 to 20, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, hydantoin epoxy resin, bisphenol A propoxy acid diglycidyl ether, bisphenol A diglycidyl ether, 1,3-bis(3-glycidyl ether propyl)tetramethyldisiloxane and 1,3,5-triglycidyl-S-triazinetrione; The carbonate is selected from one or a mixture of two of dialkyl carbonates having 1 to 18 carbon atoms, dicyclohexyl carbonate, diphenyl carbonate, methyl trifluoroethyl carbonate, ethyl trifluoroethyl carbonate, methyl ethyl ether trifluoroethyl carbonate and bistrifluoroethyl carbonate.

6. The three-component synthesis method of polyphosphonate according to claim 1, characterized in that: The molar ratio of the RP(=O)OH2 type phosphonic acid to the monoepoxy compound is 1:(2-200); The molar ratio of the active functional groups in the third component to the alcoholic hydroxyl groups in the phosphonate functionalized polyether diol is 1:(1-1.2); the Lewis acid-base catalyst is composed of an organic base and an alkyl boron; the molar ratio of the active functional groups, the organic base and the alkyl boron in the third component is 1:(0.005-2):(0.005-5); the active functional groups include isocyanate groups, epoxy groups and carbonate groups.

7. The three-component synthesis method of polyphosphonate according to claim 6, characterized in that: The organic base is selected from at least one of tertiary amines, amidines, guanidines, triaminophosphines, phosphazene bases, lithium / sodium / potassium / cesium tert-butoxide, lithium / sodium / potassium / cesium / ammonium pivalate, ionic compounds containing thiourea, ionic compounds containing urea, and ionic compounds containing carbamates; The alkyl boron is selected from at least one of B-isopinocampheyl-9-borabicyclo[3.3.1]nonane, tri-sec-butylborane, triisopropylborane, trimethylborane, tri(straight-chain) alkylborane having 2 to 8 alkyl carbon atoms, diethylmethoxyborane and trimethyl borate.

8. The three-component synthesis method of polyphosphonate according to claim 1, characterized in that: The polymerization reaction is carried out in bulk or in an organic solvent, wherein the organic solvent is a mixture of one or more of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, n-hexane, cyclohexane, acetone, ethyl acetate and tert-butanol; and the initial concentration of the monoepoxide is 5 to 20 mol / L.

9. The three-component synthesis method of polyphosphonate according to claim 1, characterized in that: The temperature of the polymerization reaction in the first step is 20-60° C., and the time of the polymerization reaction in the first step is 0.5-48 hours; the temperature of the stepwise polymerization reaction in the second step is 20-60° C., and the time of the stepwise polymerization reaction in the second step is 1-120 hours.

10. The three-component synthesis method of polyphosphonate according to claims 1-9, characterized in that: The two-step reaction can be carried out continuously in the same reactor without the need to separate and purify the intermediate product phosphonate functionalized polyether diol. Alternatively, the phosphonate functionalized polyether diol can be separated and purified before the second step polymerization reaction.

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