KR101600896B1 - Norbornene-Based Compounds with High Energy and Uses Thereof - Google Patents

Abstract

The present invention relates to a novel high-energy norbornene-based compound and a high-energy plasticizer composition comprising the same. The norbornene-based compound of the present invention has high energy density by comprising a ring strain energy group in which an energy group is contained, and low volatility. In addition, the norbornene-based compound of the present invention has viscosity less than or equal to 66 centi -poise (cP) at 25°C and a low phase transition temperature. Therefore, the plasticizer composition comprising the norbornene-based compound of the present invention has excellent physical properties and stability capable of functioning as a high-energy plasticizer without modifying a filler, thereby being able to be effectively applied to gunpowder (composite gunpowder) or a propellant.

Description

Norbornene-based compounds and their uses {Norbornene-Based Compounds with High Energy and Uses Thereof}

The present invention relates to a novel norbornene-based compound and a high-energy plasticizer composition containing the same.

Various attempts have been made to improve performance by including energy in binder used in explosives and propellants. For this purpose, a high energy functional group such as a nitro group has been introduced into a plasticizer to be added for enhancing physical properties (Reference: Korean Patent No. 10-0967848, Korean Patent No. 10-0365648). It was also possible to increase the energy by introducing an energy group such as nitro in the plasticizer added to improve the physical properties. However, most of the gunpowder is a polar material and the plasticizer including the nitro group is also polar. Plasticizers exhibiting such polarity are vulnerable to stability and may cause modification of the powder, which has the problem of deteriorating physical properties and stability of the final product. Accordingly, in order to eliminate the deformation of the powder filler during the manufacture of the product, a polar plasticizer should be avoided or replaced with a non-polar plasticizer. There are commonly used non-polar plasticizers such as DOA and DOP, but they do not contain energy groups.

On the other hand, the composite explosive developed to simultaneously improve the performance and insensitivity of the explosive is composed of a binder system composed of a granular molecular agent, a polymer and a plasticizer, and the binder system occupies about 2-20 wt% Giving the dimensional stability and insensitivity (or sensitivity) of the molecular gunpowder. Since the properties of the molecular gunpowder are determined from the chemical structure of the plasticizer used (in particular, the energy plasticizer), a more effective energy plasticizer is required.

As described above, the development of a non-polar / high energy plasticizer for improving explosive performance by improving the performance (for example, physical properties and stability) of explosives has been an important issue in the art.

Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

The present inventors have sought to develop a novel nonpolar high energy plasticizer that does not cause deformation of the filler during the processing of explosives or propellants. As a result, the present inventors synthesized / identified a novel nonpolar high-energy norbornene-based compound using a norbornene compound and an alcohol, and found that the compounds contain a high energy group in the form of a multi-ring and do not exhibit polarity , And can be effectively used as a high-energy plasticizer which does not cause deformation of the filler in the process of explosives or propellants due to its excellent thermal / chemical properties.

Accordingly, an object of the present invention is to provide a nonpolar high energy norbornene-based compound.

Another object of the present invention is to provide a high energy plasticizer composition.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention, the present invention provides a nonpolar high energy norbornene-based compound.

According to another aspect of the present invention, the present invention provides a high energy plasticizer composition comprising at least one norbornene-based compound selected from the group consisting of the norbornene-based compounds described above.

The present inventors have sought to develop a novel non-polar high energy plasticizer which does not cause deformation of the filler during processing of explosives or propellants. As a result, the present inventors synthesized / identified novel nonpolar high energy norbornene-based compounds using norbornene compounds and alcohols, and found that these compounds contain high-energy groups in the form of multiple rings and do not exhibit polarity, It is confirmed that the present invention can be effectively used as a high energy plasticizer which does not cause the deformation of the filler in the process of the explosive or propellant.

The present invention provides novel non-polar high energy plasticizers having high energy and stability by introducing a multi-ring structure. The present inventors synthesized a multicyclic compound through norbornene, various alcohols (for example, Chemical Formulas 2 to 7), and a transition metal catalyst, and synthesized a nonpolar multibranched high energy compound through an esterification reaction.

Specifically, the nonpolar high energy plasticizer of the present invention is a norbornene-based compound represented by the following general formulas (I) to (VI)

(I)

≪ RTI ID = 0.0 &

(III)

(IV)

(V)

(VI)

The process for preparing the norbornene compound of the present invention is as follows. Briefly, the norbornene-based compound of the present invention comprises: (a) performing an esterification reaction using norbornene as a raw material and an alcohol compound; And (c) separating and purifying the synthesized reaction mixture. More specifically, the norbornene-based compound of the present invention comprises the steps of: (a) dissolving a norbornene-based compound and tetrahydrofuran in an organic solvent at a molar ratio of 1:10 at room temperature; (b) adding an alcohol compound having ring tension energy to the mixture and paratoluene sulfonic acid and stirring the mixture at a high temperature (for example, 60 ° C) for 12 hours to prepare a norbornene compound of the present invention; And (c) separating and purifying the synthesized reaction mixture. The above process has a merit that a high-energy plasticizer capable of controlling energy using alcohol including various ring tensions can be manufactured easily and efficiently in the process of producing a high-energy plasticizer.

The norbornene-based compound of the present invention is a non-polar high energy compound containing no high polarity and containing a high energy group. Typically, the plasticizer is selected from the group consisting of phthalate-based (e.g., DBP, DOP, etc.), adipate based (e.g., DOA, BXA, etc.), polyether based (e.g., PS-700, RS-705, (E.g., PN-150, PN160, etc.). For example, DOA or DOP, well known as conventional nonpolar plasticizers, are similar to the norbornene-based compounds of the present invention in that they have a diester form, but do not contain an energy group and can be used in practical applications (e.g., explosives or propellants) Compared with the norbornene-based compound of the formula (I). That is, the present inventors have synthesized / identified a novel non-polar high energy compound through trans esterification reaction with alcohols containing various energy groups, mainly norbornene compounds containing multiple rings, and found that these compounds are effective And has excellent physical properties and stability that can be effectively applied as a component. The nonpolar high-energy norbornene-based compound of the present invention contains a multi-ring type energy group and functions as a high energy plasticizer which does not promote the deformation of the filler while the energy density is high, including multiple rings containing an energy group without polarity .

In some embodiments of the present invention, the norbornene-based compound includes a ring strain energy group and has low volatility.

In certain embodiments of the present invention, the norbornene-based compounds, more specifically the norbornene-based compounds of Formulas I-IV, exhibit a viscosity of less than 66 cP (centi-poise) at 25 ° C, And has a glass transition temperature (T _g ). In some embodiments of the present invention, the norbornene-based compound exhibits a decomposition temperature (T _d ) ranging from 210 ° C to 280 ° C.

The present invention provides a plasticizer composition comprising one or more of the above-mentioned norbornene-based compounds as an active ingredient.

In some embodiments of the present invention, the nonpolar norbornene-based compound of the present invention may be included in an amount of 1 wt% to 99 wt% (wt%) based on the total weight of the plasticizer composition.

In some embodiments of the present invention, the plasticizer composition of the present invention can be used as a binder in propellants or propellants.

In order to improve the performance and insensitivity of the gunpowder, the binder system (polymer and plasticizer) in the combined gunpowder composed of the granular molecular agent and the binder system is used at about 2% to 20% by weight based on the total weight of the gunpowder, It is common to use about three times as much as the polymer. It is also desirable to use a high-energy plasticizer to maximize the performance of the gunpowder. However, a conventional high-energy plasticizer (for example, an energy plasticizer containing a large amount of explosive groups such as a nitro group, a nitrate group or an azido group containing PGN (polyglycidyl nitrate)) has a high energy density but has a polarity In the preparation of a gunpowder, a predetermined molecular agent is dissolved in the plasticizer and crystallized again according to the process of lowering the temperature to room temperature after the mixing process (for example, the mixing process carried out at 60 ° C) between the molecular gunpowder and the plasticizer, (E.g., a needle) in a crystalline form (e.g., polygonal) of the crystal structure (e.g. Thus, the modified molecular gunpower can cause a change (increase) in the sensitivity of the final gunpowder product (e.g., compound gunpowder). That is, the performance and insensitivity of the gunpowder are reduced. As used herein, the term " sensitivity " refers to the ability of a gunpowder to ignite and explode in response to undesired disordered physical phenomena, such as external heat or shock, and insensitivity to the opposite nature . Since the plasticizer containing the norbornene-based compound of the present invention has a high energy density and a low viscosity (for example, 66 cP or less) and exhibits a non-polarity, it is possible to dissolve the molecular gunpowder in the above- Is very low. As a result, the plasticizer composition containing the norbornene-based compound of the present invention can minimize the shape change of the molecular gunpowder while having high energy density.

In some embodiments of the present invention, when the plasticizer composition of the present invention is used in an explosive, it is present in an amount of 1-15 wt%, more specifically 3-10 wt%, and more specifically 5-8 wt% ≪ / RTI >

When the plasticizer composition of the present invention is used in a propellant, it may be contained in an amount of 1-20% by weight, more specifically 2-15% by weight, based on the total weight. Typically, the propellant composition comprises (i) a binder; (ii) an oxidizing agent or raw gunpowder; And (iii) an additive. The binder is a material forming a rubber matrix structure in the propellant composition, and the cross-linking is reversibly changed depending on temperature, for example, a thermoplastic elastomer binder. In addition, the oxidizing agent or the starting powder may be included in an amount of about 70-85% by weight based on the total weight. The oxidizing agent is not particularly limited as long as it is well known in the art, for example, 1,7-diazido-2,4,6-trinitrazaheptane, DATH ), Ammonium dinitramide (ADN), ammonium chlorate, ammonium nitrate (AN), ammonium perchlorate (AP), cesium nitrate hydroxyl ammonium nitrate nitrate, hydroxylammonium nitrate, HAN), hydrazinium nitrate (HN), hydroxylammonium perchlorate, potassium chlorate, potassium perchlorate, potassium nitrate ), Lithium nitrate, lithium perchlorate, sodium chlorate, sodium perchlorate, and sodium nitrate It includes (sodium nitrate). The raw material powder is not particularly limited as long as it is known in the art, and examples thereof include 1,1-diamino-2,2-dinitro-ethylene, FOX-7), 1,2,4-trinitrobenzene, 1,3,3-trinitroazetidine (TNAZ), 1,3,4 , 1,3,4,6-tetranitroglycoluril, cyclotetramethylene tetranitramine (HMX), 1,3,5-triamino-2,4,6-trinitrobenzene ( 1,3,5-triamino-2,4,6-trinitrobenzene, TATB), cyclotrimethylenetrinitramine (RDX), 1,3,5-trinitrobenzene (TNB) , 1,3-diamino-2,4,6-trinitrobenzene (DATB), 2,2 ', 4,4', 6,6'-hexane (2,2 ', 4,4', 6,6'-hexanitroazobenzene, HNAB), 2,2 ', 4,4', 6,6'-hexanenitrodiphenyl 4 ', 6,6'-hexanitrodiphenyl, HNDP), hexanitrohexa Which comprises hexanitrohexaazaisowurtzitane (CL-20), trinitrotoluene (TNT), picric acid, tetryl and oxynitrotriazole (NTO) Can be used.

The additive may include at least one additive selected from the group consisting of a metal powder, a burn rate modifier, a coolant, a plasticizer, a binder, an antioxidant, a stabilizer, and a processing aid. In particular, plasticizers may be included to change the combustion characteristics or mechanical properties of the propellant.

In some embodiments of the present invention, the plasticizer composition of the present invention may additionally contain other plasticizers or energy-free plasticizers that contain energy in addition to the norbornene-based compounds of the present invention. For example, other plasticizers that contain energy include glycerol-2,4-dinitrophenylether dinitrate, trimethylolethylmethane trinitrate (TMPTN), glycerol- Energy-free plasticizers, including, but not limited to, nitroglycerine, 1,2,4-butanetriol trinitrate, TMETN and butyl nitroxyethylnitramine (BTNN), include dibutyl phthalate (DBP), dioctyl adipate (DOA), dioctyl phosphate (DOP), isodecyl pelargonate (IDP), and trioctyl phosphate (TOP) But is not limited thereto.

The features and advantages of the present invention are summarized as follows:

(a) The present invention relates to a novel non-polar high-energy norbornene-based compound and a high-energy plasticizer containing the same.

(b) The norbornene-based compound of the present invention not only has high energy density but also low volatility, including a ring tension energy group containing an energy group.

(c) Further, the norbornene-based compound of the present invention has a viscosity of less than 66 cP (centi-poise) at 25 DEG C and a low phase transition temperature.

(d) Therefore, the plasticizer composition containing the norbornene-based compound of the present invention has excellent physical properties and stability capable of functioning as a high-energy plasticizer that does not progress the deformation of the filler and is effectively applied to a powder (for example, a composite powder) .

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Reagents and Materials

The present invention relates to a process for the preparation of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry, Japan), 2-ethylhexanol (Tokyo Chemical Industry, Japan), Nonanoic acid (Sigma Aldrich, (Sigma Aldrich, USA), tetrahydrofuran (Burdick and Jackson, USA), benzene (daejung, (Duksan, Korea), anhydrous magnesium sulfate (Samchun, Korea), nucleic acid (duksan, Korea) and ethyl acetate (duksan, Korea) were used.

NMR  analysis

^{The 1} H and ¹³ C NMR spectra were obtained using a Bruker Advance II / DPX 400 MHz (400 MHz ¹ H, 100 MHz ¹³ C) NMR. Briefly, ¹ H NMR spectra were obtained by subjecting a chemical shift to a multiplicity (br = broad, s = singlet, d = doublet, t = triplet) with trichloromethane-D (δ 7.26 ppm) as an internal standard , q = quartet, m = multiplet). ^{The 13} C NMR spectrum was obtained by chemical shifts using trichloromethane-D (? 77.26 ppm) as an internal standard.

Property measurement

The viscosity of each compound was measured at 25 DEG C using a VROC viscometer from micro VISC ^TM . The glass transition temperature (T _g ) was determined by DSC analysis using SHIN DO 2920 (TA Instruments, USA). Thermogravimetric analysis was performed using a TGA 2050 (Seiko Instruments, Japan) And the decomposition temperature (T _d ) was determined.

Synthesis of raw materials

The present invention relates to a process for synthesizing a nonpolar high energy plasticizer having a ring tension energy using norbornene as a center, and also a transition metal catalyst [carbonyldihydridotris (triphenylphosphine) ruthenium (II)] and alkene, and then synthesizing other nonpolar high energy plasticizers using the general formulas (4) and (5). The physical properties of the synthesized compounds are low in viscosity and glass transition temperature and high in pyrolysis temperature, and exhibit characteristics including a ring tension energy group similar to that of a general nonpolar plasticizer. The plasticizer can be obtained by modifying a norbornene-based compound and esterifying it with various alcohols. The norbornene compound used in the above reaction was easily synthesized from readily available starting materials, and the compound of formula (5) was synthesized by a generally known synthesis method.

rescue rescue Formula 1

(2)

(3)

Formula 4

Formula 5

6

Formula 7

8

Formula 9

Norbornene and alcohols used in the present invention.

The reaction using the above compound is shown in the following Reaction Scheme 1 and Reaction Scheme 2 for the norbornene system:

Scheme 1 shows the synthesis of the plasticizer through the esterification reaction of the compound of Formula 1 and the reaction of Formula 2 as the starting material.

[Reaction Scheme 1]

Scheme 2 also shows a synthesis method of nonpolar multibranched high energy plasticizer through synthesis of norbornene in the form of polycyclic rings using a transition metal catalyst and transesterification using alcohol.

[ Scheme 2 ]

rescue rescue NOR -One

NOR -2

NOR -3

NOR -4

NOR -5

NOB -One

NOB -2

DNOB -One

DNOB -2

Compounds synthesized / identified in the present invention.

On the other hand, in order to be used as a plasticizer, a liquid having a low viscosity and low volatility should have a low phase transition temperature and viscosity, and a high density is preferable. The physical properties of the synthesized plasticizers were measured through viscosity measurement, DSC and TGA analysis. The heat of formation for each material can be calculated using the Gauss-03 series program (based on the theory BP86 / 6-31 ^** (Optimum geometry is adopted and shape analysis is used to select the lowest energy state structure Set), and the properties and energy calculations are shown in Table 3 below (see Example 10).

[Reaction Scheme 1] Ring tension  included Nobonen  Specific details of system synthesis Example

Example  One: Dioctyl Bicyclo [2.2.1] hept -5-ene-2,3- Dicarboxylate ( NOR -One)

0.82 g (4.95 mmole) of 5-norbornene-2,3-dicarboxylic anhydride was dissolved in 5 mL of tetrahydrofuran and 25 mL of benzene solvent, and then 6.50 g (49.45 mmole) of octanol and 0.29 g (1.49 mmole) of paratoluenesulfonic acid was added and reacted at 60 ° C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. 1.54 g (3.8 mmole, 5-norbornene-2,3-dicarboxylic acid) was obtained through column separation (nucleic acid: ethyl acetate = 50: NOR-1 was obtained at a yield of 77.0% considering the molecular weight of the hydride.

The NMR analysis results for the NOR-1 compound are as follows:

^{1 H NMR (400 MHz, CDCl} 3) δ 6.23 (t, 2H, J = 1.6), 4.04-3.89 (m, 4H), 3.26 (t, 2H, J = 1.2), 3.14 (s, 2H), 1.58 -1.53 (m, 4H), 1.31-1.26 (m, 22H), 0.88-0.85 (m, 6H).

^{13 C NMR (100 MHz, CDCl} 3) δ 172.7, 135.0, 64.7, 48.8, 48.4, 46.5, 32.0, 29.45, 29.42, 28.7, 26.1, 22.8, 14.2.

Example 2: Synthesis of bis (2-ethylhexyl) bicyclo [2.2.1] hept-5-ene-2,3-carboxylate (NOR-

0.82 g (4.95 mmole) of 5-norbornene-2,3-dicarboxylic anhydride was dissolved in 5 mL of tetrahydrofuran and 25 mL of benzene solvent, and 6.44 g (49.45 mmole) of 2-ethylhexane And 0.29 g (1.50 mmole) of paratoluenesulfonic acid were added thereto, and the mixture was reacted at 60 DEG C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. Then, 1.11 g (2.75 mmole, 5-norbornene-2,3-dicarboxylic acid) was obtained through column separation (nucleic acid: ethyl acetate = 50: NOR-2 was obtained with a yield rate of 55.0% considering the molecular weight of the hydride.

The NMR analysis results for the NOR-2 compound are as follows:

^{1 H NMR (400 MHz, CDCl} 3) δ 6.23 (s, 2H, J = 1.6), 4.01-3.78 (m, 4H), 3.27 (t, 2H, J = 1.2), 3.15 (s, 2H), 1.53 -1.49 (m, 2H), 1.36-1.26 (m, 18H), 0.93-0.88 (m, 12H).

^{13 C NMR (100 MHz, CDCl} 3) δ 172.8, 135.0, 67.08, 62.02, 48.9, 48.3, 46.6, 38.8, 30.65, 30.61, 29.16, 29.12, 24.0, 23.9, 24.0, 23.9, 23.2, 14.2, 11.1.

Example 3: Bis (cyclobutylmethyl) bicyclo [2.2.1] hept-5-ene-2,3-carboxylate (NOR-

0.82 g (4.95 mmole) of 5-norbornene-2,3-dicarboxylic anhydride was dissolved in 5 mL of tetrahydrofuran and 25 mL of benzene solvent, and 4.30 g (49.45 mmole) of cyclobutyl methanol 0.29 g (1.50 mmole) of paratoluenesulfonic acid was added and reacted at 60 DEG C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. 1.07 g (3.8 mmole, 5-norbornene-2,3-dicarboxylic acid) was isolated via column separation (nucleic acid: ethyl acetate = 50: Yield of 68.0% in consideration of the molecular weight of the hydride) NOR-3 was obtained.

As described above, the present invention can synthesize bicyclo [2.2.1] heptenediyl methanol through reduction reaction from 5-norbornene-2,3-dicarboxylic anhydride, and using this, a ring- High - energy plasticizer is synthesized and its synthesis method is suggested.

Example 4: Bicyclo [2.2.1] hept-5-ene-2,3-diylbis (methylene) carboxylate (NOR-

After dissolving 0.50 g (3.24 mmole) of bicyclo [2.2.1] heptenediyl methanol in 3 mL of tetrahydrofuran and 15 mL of benzene solvent, 2.56 g (16.21 mmole) of nonanoic acid and 0.18 g (0.97 mmole) Of paratoluenesulfonic acid was added and reacted at 60 DEG C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.49 g (1.13 mmole, biscyclo [2.2.1] heptenediyl methanol) by column separation (nucleic acid: ethyl acetate = 50: Yield: 35.0%) of NOR-4.

The NMR analysis results for the NOR-4 compound are as follows:

^{1 H NMR (400 MHz, CDCl} 3) δ 6.16 (s, 2H), 3.91-3.73 (m, 4H), 2.90 (s, 2H), 2.51 (s, 2H), 2.31-2.26 (m, 4H), 1.63-1.50 (m, 6H), 1.34-1.23 (m, 20H), 0.89-0.85 (m, 6H).

^{13 C NMR (100 MHz, CDCl} 3) δ 173.6, 135.4, 64.3, 48.9, 45.4, 40.6, 34.4, 31.8, 29.2, 29.16, 29.12, 25.0, 22.6, 14.0.

Example  5: Bicyclo [2.2.1] hept -5-ene-2,3- Di-bis (methylene) dicyclobutane  Carboxylate ( NOR -5)

0.50 g (3.24 mmole) of bicyclo [2.2.1] heptenediyl methanol was dissolved in 3 mL of tetrahydrofuran and 15 mL of benzene solvent, and then 1.60 g (16.21 mmole) of cyclobutanecarboxylic acid and 0.18 g ) Para-toluenesulfonic acid was added thereto and reacted at 60 DEG C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to obtain 0.93 g (1.13 mmole, biscyclo [2.2.1] heptenediyl methanol) by column separation (nucleic acid: ethyl acetate = 50: Yield: 90.0%) of NOR-5 was obtained.

The NMR analysis results for the NOR-5 compound are as follows:

^{1 H NMR (400 MHz, CDCl} 3); δ 4.01 (d, 4H, J = 6.8 Hz), 2.99-2.93 (m, 2H), 2.62-2.54 (m, 2H), 2.30-2.16 (m, 8H), 2.07-1.99 (m, 4H), 1.93 -1.81 (m, 4H), 1.77-1.71 (m, 4H).

^{13 C NMR (100 MHz, CDCl} 3); [delta] 175.7, 68.4, 38.1, 37.6, 37.0, 34.3, 33.1, 24.9, 24.8, 18.6.

[Reaction Scheme 2] Ring tension  included Nobonen  Specific details of system synthesis Example

(Carbonyldihydridotris (triphenylphosphine) ruthenium (II)) from the norbornene in the following specific examples of the synthesis of the norbornene-based compound containing a ring- And alkene were synthesized, and a high-energy plasticizer containing a cyclic group was synthesized by using the synthesized cyclic compound (Reference Examples 6 to 9).

Example  6: bis (2- Ethylhexyl ) Tricyclo [4.2.1.0 ^2.5 ] Non-3-ene-3,4- Dicarboxylate ( NOB -One)

A solution of 1.10 g (4.66 mmole) of dimethyltricyclo [4.2.1.0 ^2,5 ] -3,4-dicarboxylate in 3 mL of tetrahydrofuran and 15 mL of benzene was dissolved in 6.12 g (46.56 mmole) Of 2-ethylhexanol and 0.91 g (4.66 mmole) of paratoluenesulfonic acid were added and reacted at 60 DEG C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.93 g (1.13 mmole, dimethyl tricyclone [4.2.1.0 ^2,5 ] -3 , And a production rate considering the molecular weight of 4-dicarboxylate: 64.0%).

The NMR analysis results for the NOB-1 compound are as follows:

^{1 H NMR (400 MHz, CDCl} 3) δ 4.12-4.02 (m, 4H), 2.64 (s, 2H), 2.22 (s, 2H), 1.60 (d, 4H, J = 6.8), 1.38-1.28 (m , 17H), 1.13-1.04 (m, 3H), 0.89 (t, 12H, J = 3.6).

^{13 C NMR (100 MHz, CDCl} 3) δ 161.6, 142.4, 67.2, 47.6, 39.0, 38.9, 34.1, 30.6, 30.5, 29.1, 28.0, 24.0, 23.1, 14.2, 11.2, 11.1.

Example  7: Bis Cyclobutylmethyl ) Tricyclo [4.2.1.0 ^2.5 ] Non-3-ene-3,4- Dicarboxylate ( NOB -2)

1.10 g (5.45 mmole) of dimethyltricyclo [4.2.1.0 ^2,5 ] -3,4-dicarboxylate was dissolved in 3 mL of tetrahydrofuran and 15 mL of benzene, and 4.05 g (46.56 mmole) Of cyclohexylmethanol and 1.05 g (4.66 mmole) of paratoluenesulfonic acid were added and reacted at 60 DEG C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. Then, 0.78 g (2.24 mmole, dimethyl tricyclone [4.2.1.0 ^2,5 ] -3 , And a production rate in consideration of the molecular weight of 4-dicarboxylate: 48.0%).

The NMR analysis results for the NOB-2 compound are as follows:

^{1 H NMR (400 MHz, CDCl} 3) δ 4.17-4.08 (m, 4H), 2.68-2.63 (m, 4H), 2.23 (s, 2H), 2.09-2.01 (m, 4H), 1.94-1.74 (m , 8H), 1.64-1.57 (m, 2H), 1.34 (d, 1H, J = 10.8), 1.13-1.04 (m, 3H).

^{13 C NMR (100 MHz, CDCl} 3) δ 161.7, 142.4, 68.5, 47.6, 34.2, 34.0, 30.6, 28.0, 24.9, 24.8, 18.6.

Example  8: Bis (2-ethylhexyl) hexahydro -3,7- Methanocyclobutane 1 , 2-dicarboxylate ( DNOB -One)

The mixture of 1.30 g (5.45 mmole) of 3,7-methano-3H-cyclo [ f ] tindine-1,2-dicarboxylic acid, 2a, 3a, 4a, 6a, 7a-hexahydrodimethyl ester dissolved in tetrahydrofuran and 15 mL of benzene, 6.23 g (54.47 mmole) of 2-ethylhexanol and 1.05 g (5.45 mmole) of paratoluenesulfonic acid were added and reacted at 60 ° C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. 0.89 g (2.18 mmole, 3,7-methano-3H-cyclobutyl [ f ] 2-dicarboxylic acid, 2a, 3a, 4a, 6a, 7, 7a-hexahydrodimethyl ester, 40.0%).

The results of NMR analysis for the DNOB-1 compound are as follows:

¹ H NMR (400 MHz, CDCl ₃ )? 5.65-5.63 (m, 1H), 5.54-5.52 (m, 1H), 4.11-4.01 (m, 4H), 3.2-3.16 1H, J = 3.2), 2.72-2.68 (m, 2H), 2.34 (d, 1H, J = 4.4), 2.27-2.21 (m, 3H), 1.62-1.57 m, 18H), 0.88 (t, 12H, J = 7.6).

^{13 C NMR (100 MHz, CDCl} 3) δ 161.5, 142.7, 141.5, 131.8, 130.9, 67.2, 67.1, 52.4, 44.4, 41.7, 41.5, 38.8, 37.8, 36.0, 34.0, 31.4, 30.5, 29.1, 23.9, 23.1 , 14.2, 11.3, 11.2.

Example  9: Bis (cyclobutylmethyl) hexahydro -3,7- Methanocyclobutaine -1,2-dicarboxylate ( DNOB -2)

The mixture of 1.30 g (5.45 mmole) of 3,7-methano-3H-cyclo [ f ] tindine-1,2-dicarboxylic acid, 2a, 3a, 4a, 6a, 7a-hexahydrodimethyl ester (54.47 mmole) of cyclomethanol and 1.05 g (5.45 mmole) of para-toluenesulfonic acid were added to the reaction mixture and reacted at 60 ° C for 12 hours. 10 mL of an aqueous solution was added to the mixed solution, and the mixture was extracted with 50 mL of ethyl ether. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. 0.92 g (2.40 mmole, 3,7-methano-3H-cyclobutane [ f ]) was obtained through column separation (nucleic acid: ethyl acetate = 50: 2-dicarboxylic acid, 2a, 3a, 4a, 6a, 7, 7a-hexahydrodimethyl ester: 44.0%).

The NMR analysis results for the DNOB-2 compound are as follows:

^{1 H NMR (400 MHz, CDCl} 3) δ 5.65-5.63 (m, 1H), 5.55-5.53 (m, 1H), 4.17-4.08 (m, 4H), 3.20-3.16 (m, 1H), 2.79 (d , 1H, J = 3.2), 2.72-2.68 (m, 4H), 2.35 (d, 1H, J = 4.4), 2.27-2.22 (m, 3H), 2.08-2.01 (m, 4H), 1.95-1.75 ( m, 8H), 1.49 (d, 1H, J = 10.4), 1.29 (d, 1H, J = 10.4).

^{13 C NMR (100 MHz, CDCl} 3) δ 161.6, 142.7, 141.5, 131.8, 131.0, 68.4, 52.4, 44.5, 41.8, 41.5, 37.9, 36.1, 34.3, 34.1, 31.4, 25.0, 24.9, 18.6.

Example  10: Properties of the compounds prepared in the present invention

The energy and physical properties of the plasticizer are very important because the plasticizer content of the high energy propellant is typically 1-20 wt% and the plasticizer content of the composite powder is about 10 wt% or less. It was confirmed that the norbornene-derived compounds (Table 2) prepared in the present invention had excellent physical properties, stability, and high energy (Table 3).

# The
(Molecular Weight) Viscosity
( cP at  25 ° C) T _d (° C) T _g (° C) density Δ H _f
( Kcal / mol ) NOR-1 C ₂₅ H ₄₂ O ₄
(406.5986) 28.1 248 -82.50 1.018 -210.8 (g)
-258.6 (s) NOR-2 C ₂₅ H ₄₂ O ₄
(406.5986) 33.8 241 -83.16 1.021 -206.1 (g)
-253.9 (s) NOR-3 C ₁₉ H ₂₆ O ₄
(318.4073) 24.0 235 -65.91 +
Phase change 0.964 -119.0 (g)
-158.4 (s) NOR-4 C ₂₇ H ₄₆ O ₄
(434.6517) 24.0 274 Measures
X 0.965 -217.7 (g)
-268.3 (s) NOR-5 C ₂₇ H ₂₈ O ₄
(416.5088) 18.9 212 - 1.086 -118.8 (g)
-158.1 (s) NOB-1 C ₂₇ H ₄₄ O ₄
(432.6359) 30.6 248 -85.86 0.971 -188.0 (g)
-238.6 (s) NOB-2 C ₂₁ H ₂₈ O ₄
(344.4446) 66.1 244 -71.14 1.087 -100.4 (g)
-142.5 (s) DNOB-1 C ₃₀ H ₄₆ O ₄
(470.6838) 316.6 250 - 1.023 -161.7 (g)
-216.6 (s) DNOB-2 C ₂₄ H ₃₀ O ₄
(382.4926) 103.5 272 -80.18 1.106 -74.9 (g)
-121.3 (s)

Properties of the Compounds of the Invention.

Abbreviation: g, gaseous state; And s, solid state.

The plasticizer of the present invention is a non-polar high energy plasticizer containing an energy group having a ring tension while maintaining a structure similar to that of a non-polar plasticizer. Therefore, since the linear structure of the norbornene-based compounds of the present invention can separate the polymer chains well, it has a suitable chemical structure as a plasticizer and does not exhibit polarity, so that deformation of the chargeable powder does not occur during processing, and the physical properties and stability Maintenance or high performance can be expected. Also, unlike general nonpolar plasticizers, they contain ring tension energy and have high energy. Therefore, the nonpolar high-energy plasticizer of the present invention is excellent in thermal / chemical properties and particularly has an advantage that it can control the energy content and can be used as a high-performance propellant. It can be used alone for a propellant or a composite explosive, It is a very promising material for mixing with plasticizers. Moreover, the compounds of the present invention are first provided as non-polar plasticizers with high energy, and the expected effect thereof is expected to be very high.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (11)

A nonpolar high energy norbornene compound represented by the following formula (II) to (VI):
≪ RTI ID = 0.0 &

(III)

(IV)

(V)

(VI)

The norbornene-based compound according to claim 1, wherein the norbornene-based compound comprises a ring strain energy group. The norbornene-based compound according to claim 1, wherein the norbornene-based compound exhibits a viscosity of less than 66 cP (centi-poise) at 25 ° C. The norbornene compound according to claim 1, wherein the norbornene compound has a glass transition temperature (T _g ) in a range of -71 ° C or lower. The norbornene-based compound according to claim 1, wherein the norbornene-based compound has a decomposition temperature (T _d ) in the range of 210 ° C to 280 ° C. A high energy plasticizer composition comprising at least one norbornene-based compound selected from the group consisting of norbornene-based compounds of the following general formula (I) and norbornene-based compounds of any one of claims 1 to 5:
(I)

. The high energy plasticizer composition of claim 6, wherein the norbornene-based compound is included in an amount of 1 to 99 wt% (wt%) based on the total weight of the plasticizer composition. 7. The high energy plasticizer composition of claim 6, wherein the plasticizer composition further comprises a plasticizer that does not contain energy or other plasticizer. 7. The high energy plasticizer composition of claim 6, wherein the plasticizer composition is used as a binder in propellants or propellants. The high energy plasticizer composition of claim 9, wherein the plasticizer composition is from 5% to 8% by weight, based on the total weight of the composition. The high energy plasticizer composition of claim 9, wherein the plasticizer composition is from 2% to 15% by weight based on the total weight of the plasticizer composition when used in a propellant.