CN110372460A - A kind of method of lattice intercalation induction FOX-7 explosive densification - Google Patents
A kind of method of lattice intercalation induction FOX-7 explosive densification Download PDFInfo
- Publication number
- CN110372460A CN110372460A CN201910712383.8A CN201910712383A CN110372460A CN 110372460 A CN110372460 A CN 110372460A CN 201910712383 A CN201910712383 A CN 201910712383A CN 110372460 A CN110372460 A CN 110372460A
- Authority
- CN
- China
- Prior art keywords
- fox
- explosive
- induction
- densification
- lattice
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
- C06B21/0016—Compounding the ingredient the ingredient being nitrocellulose or oranitro cellulose based propellant; Working up; gelatinising; stabilising
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of methods of lattice intercalation induction FOX-7 explosive densification, are related to advanced composite material (ACM) preparation technical field.This method deficiency low towards FOX-7 lattice bulk density, choosing a kind of high nitrogen two-dimensional material is intercalated molecule, obtains a kind of FOX-7 base novel high-desity explosive of two-dimensional material intercalation modifying.Specific steps are as follows: step 1: by high nitrogen two-dimensional polymer monomer and 1,1- diamino -2,2- dinitro ethylene (FOX-7) is added a kind of organic solvent with a certain concentration according to a certain ratio, is heated to certain temperature；Step 2: organic aldehyde solution being added in hot solution described in step 1, the temperature of step 1 is maintained, and reacts certain time under certain stirring rate；Step 3: the anti-solvent isometric with solvent is added in step 2 is precipitated product；Obtained product can obtain high density FOX-7 based composites after centrifugation and drying.
Description
Technical field
The invention belongs to advanced composite material (ACM) preparation technical fields, and in particular to a kind of lattice intercalation induction FOX-7 explosive
The method of densification.
Background technique
As a kind of insensitive explosives having wide application prospects, 1,1- diamino -2,2- dinitro ethylene (FOX-7) is first
By Latypov et al. report synthesize, and elaborate its may replace RDX be used for insensitive munitions a possibility that [Propellants,
Explos.Pyrotech.1993,18,1].The molecular configuration of FOX-7 be wavy layer structure, between layers mainly by
Hydrogen bond is constituted, when by environmental stimuli, interlayer mutually slide can buffer portion external carbuncle, therefore with preferably security performance
[explosive wastewater journal, 2009,32:6].But lead to its lattice since there is waveform crystal structure larger inner space not to be filled
Accumulation degree is not high, the lower (1.885g/cm of crystalline density3), therefore the detonation property of FOX-7 still has room for promotion.
Number of ways can be used for being promoted the crystalline density of energetic material, including U.S.'s benefit limit that not mole laboratory is reported
Under the conditions of compression test, illustrate compression crystals space to the affecting laws of density.But in practical operation, this method is difficult
To realize on a large scale, and higher cost.In recent years, two-dimensional material modification is given in the development of two-dimensional material Subjective and Objective intercalation technique
Opportunity is provided, the core of the technology is that the gap of lattice each other is filled up by way of the mutual intercalation of lattice.Chinese patent
[CN107540019B] and [CN109502578A] has developed a kind of molybdenum disulfide/graphene and vanadium oxide nanometer sheet/stone respectively
The preparation method of black alkene alternating intercalation configuration material, above two report confirms can be by lattice intercalation shape between two-dimensional material
At complementation, but do not refer to that density enhances related data.Chinese patent [CN108530104A] describes gives birth in situ under a kind of high temperature
Long graphene/boron nitride nano-tube ceramic matric composite densifying method, this method elaborate graphene and two kinds of boron nitride
The mutual intercalation of two-dimensional material is associated with densification.Yang Quanhong et al. [CN108364801A] has invented a kind of graphene-based densification
The preparation method of composite material, the densification that this method first passage ermal physics control measures realize graphene-based material change
Property.Yan Qilong et al. [CN108424339A] has invented a kind of preparation method of high density octogen (HMX), and this method passes through
The crystalline growth for constraining HMX realizes densification.
The new technology that these new concepts cause, which all has the preparation with lattice intercalation characteristic FOX-7 base explosive, centainly borrows
Mirror meaning.From the point of view of existing open source information, the two-dimensional material of lattice intercal type is prepared there are still process flows complicated, cost mistake
Height is difficult to the problems such as amplifying, meanwhile, there has been no the reports that lattice intercalation modifying technology is used for FOX-7 densification.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, provide a kind of side of lattice intercalation induction FOX-7 explosive densification
Method.Core of the invention is to choose lattice intercalator of this novel energetic material of high nitrogen two-dimensional polymer as FOX-7, adopt
It is obviously improved with the technological means of Subjective and Objective intercalation preparation density and safety still maintains the novel FOX-7 base of low sense characteristic fried
Medicine.In view of the above problem of the prior art, according to one aspect of the present disclosure, the invention adopts the following technical scheme:
To achieve the goals above, the invention adopts the following technical scheme:
A kind of method of lattice intercalation induction FOX-7 explosive densification, comprising the following steps:
Step 1: by high nitrogen two-dimensional polymer monomer and 1,1- diamino -2,2- dinitro ethylene (FOX-7) according to mole
Than organic solvent is added for 1:3~1:10, heating obtains hot solution；
Step 2: organic aldehyde solution being added in hot solution described in step 1, the heating temperature in step 1 is maintained, while stirring
It mixes side to react 10 minutes~120 minutes, obtains mixed liquor；
Step 3: the anti-solvent isometric with solvent, which is added, into the mixed liquor that step 2 obtains is precipitated product；It obtains
Product obtains high density FOX-7 based composites after centrifugation and drying.
As preferred: in the step 1, the high nitrogen two-dimensional polymer monomer is triaminoguanidine hydrochloride or triamido
Guanidine nitrate.
As preferred: in the step 1, the total concentration range of the high nitrogen two dimension and FOX-7 be 50mg/mL~
150mg/mL。
As preferred: in the step 1, the organic solvent is dimethyl sulfoxide, N, N- dimethyl imide or chlorine
Change sulfoxide, the heating temperature is 70 DEG C~110 DEG C.
As preferred: in the step 2, the organic aldehyde solution is formaldehyde, acetaldehyde or the second two of mass fraction 37%
Aldehyde.
As preferred: in the step 2, the molar ratio of high nitrogen two-dimensional polymer monomer and organic aldehyde is 1:2.
As preferred: in the step 2, stirring rate is 100rpm~1000rpm.
As preferred: in the step 3, the anti-solvent is deionized water, methanol or ethyl alcohol, and dosage is and step
Organic solvent in 1 is isometric.
Compared with the prior art, the invention has the beneficial effects that:
The preparation method of a kind of lattice intercalation induction FOX-7 densification proposed by the present invention, before high nitrogen two-dimensional polymer
It is that raw material is blended in a kind of organic solvent that body, which is driven, with FOX-7, uses organic aldehyde solution for crosslinking agent, in a manner of anti-solvent is added
Make FOX-7 along high nitrogen two-dimensional polymer growth in situ, finally obtains a kind of FOX-7 base novel material containing energy of lattice intercalation modifying
Material.
Preparation method according to the present invention has a characteristic that 1. simple process, the cost of raw material be lower, condition temperature
It is strong and product morphology is uniform with universality；2. composite micro-structure can be regulated and controled with performance by controlling reaction condition；③
High nitrogen two-dimensional polymer itself loses the energy density of FOX-7 containing energy, not.The result shows that the addition of high nitrogen two-dimensional polymer is aobvious
Work improves FOX-7 explosive crystal density, and the present invention is of great significance to the detonation property for promoting insensitive explosives.
This method compared with prior art, beneficial effects of the present invention first is that: prepared FOX-7 base explosive not only has
There is high crystalline density, and impact sensitivity is lower, is a kind of with the safety-high energy characteristic New Explosives.The invention institute
The pattern for obtaining product is uniform, and preparation process is simple, is easy to amplify, favorable reproducibility, yield is up to 95% or more.The present invention is also it
The densification of its low sense explosive provides a kind of new methods and techniques approach.
Detailed description of the invention
Illustrate present specification embodiment or technical solution in the prior art in order to clearer, it below will be to embodiment
Or attached drawing needed in the description of the prior art is briefly described, it should be apparent that, the accompanying drawings in the following description is only
It is the reference to embodiments some in present specification, for those skilled in the art, what is do not made the creative labor
In the case of, other attached drawings can also be obtained according to these attached drawings.
Fig. 1 is the preparation flow figure of the high density FOX-7 explosive prepared according to the embodiment of the present invention 1；
Fig. 2 is the plane domain scanning electron microscope of the high density FOX-7 explosive prepared according to the embodiment of the present invention 1
Figure；
Fig. 3 is the fringe region scanning electron microscope of the high density FOX-7 explosive prepared according to the embodiment of the present invention 1
Figure.
Specific embodiment
The present invention will be further described with reference to the examples below, and described embodiment is only present invention a part
Embodiment is not whole embodiment.Based on the embodiments of the present invention, those skilled in the art are not making
Other embodiments used obtained, belong to protection scope of the present invention under the premise of creative work.
Embodiment 1
The triaminoguanidinium nitrate of 0.36g and the FOX-7 of 2.25g are weighed, 45mL dimethyl sulfoxide is added to reactant
In (at this time solute concentration be 58mg/mL), being heated to 105 DEG C is uniformly mixed reactant；The glyoxal of 0.41g is added above-mentioned
Hot solution is stirred to react after sixty minutes under 500rpm revolving speed, obtains mixed liquor；45mL deionized water is added into mixed liquor makes product
It is precipitated；Finally, product can obtain high density FOX-7 based composites after filtering, deionized water washing, vacuum drying, and yield is
98.7%.
The process signal of high density FOX-7 based composites prepared by example 1 is as shown in Figure 1.
High density FOX-7 based composites prepared by example 1 are scanned electron microscope (SEM) observation, scanning electricity
Sub- microscopy images are as shown in Figures 2 and 3.As seen from the figure, FOX-7 crystal Compound Degree is preferable, does not find that individually two dimension is altogether
Conjugated material body, and crystal structure is fine and close, plane configuration is obvious.
High density FOX-7 based composites prepared by example 1 carry out vacuum density analysis, density using gas displacement method
Test result is 1.9826g/cm3。
Embodiment 2
The triaminoguanidine hydrochloride of 0.36g and the FOX-7 of 0.96g are weighed, 13mL thionyl chloride is added in reactant
(solute concentration is 102mg/mL at this time), being heated to 70 DEG C is uniformly mixed reactant；The formalin of 0.58g is added above-mentioned
Hot solution obtains mixed liquor after 100rpm is stirred to react 120 minutes；13mL deionized water is added into mixed liquor is precipitated product；
Finally, product can obtain high density FOX-7 based composites, yield 96.9% after filtering, deionized water washing, vacuum drying
High density FOX-7 composite material prepared by example 2 carries out vacuum density analysis using gas displacement method, and density is surveyed
Test result is 1.9013g/cm3。
Embodiment 3
The triaminoguanidine hydrochloride of 0.36g and the FOX-7 of 3.19g are weighed, by 24mL N, N- dimethyl imide is added to
In reactant (solute concentration is 147mg/mL at this time), being heated to 110 DEG C is uniformly mixed reactant；By the glyoxal of 0.41g
Above-mentioned hot solution is added in solution, and 1000rpm is stirred to react after ten minutes, obtains mixed liquor；24mL is added into mixed liquor without water beetle
Product is precipitated in alcohol water；Finally, product can obtain high density FOX-7 base composite wood after filtering, deionized water washing, vacuum drying
Material, yield 97.6%.
High density FOX-7 composite material prepared by example 3 carries out vacuum density analysis using gas displacement method, and density is surveyed
Test result is 1.9125g/cm3。
Embodiment 4
The triaminoguanidinium nitrate of 0.36g and the FOX-7 of 1.44g are weighed, 25mL dimethyl sulfoxide is added to reactant
In (at this time solute concentration be 72mg/mL), being heated to 90 DEG C is uniformly mixed reactant；The glyoxal solution of 0.42g is added
Above-mentioned hot solution obtains mixed liquor after 700rpm is stirred to react 90 minutes；25mL dehydrated alcohol water is added into mixed liquor makes product
It is precipitated；Finally, product can obtain high density FOX-7 based composites after filtering, deionized water washing, vacuum drying, and yield is
97.9%.
High density FOX-7 composite material prepared by example 4 carries out vacuum density analysis using gas displacement method, and density is surveyed
Test result is 1.9301g/cm3。
Embodiment 5
The triaminoguanidinium nitrate of 0.36g and the FOX-7 of 2.25g are weighed, 23mL dimethyl sulfoxide is added to reactant
In (at this time solute concentration be 113mg/mL), being heated to 100 DEG C is uniformly mixed reactant；The glyoxal of 0.41g is added
Hot solution is stated, is stirred to react under 400rpm revolving speed after forty minutes, obtains mixed liquor；23mL deionized water is added into mixed liquor to be made to produce
Object is precipitated；Finally, product can obtain high density FOX-7 based composites, yield after filtering, deionized water washing, vacuum drying
It is 98.0%.
High density LLM-105 composite material prepared by example 5 carries out vacuum density analysis, density using gas displacement method
Test result is 1.9537g/cm3。
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with it is other
The difference of embodiment, the same or similar parts in each embodiment cross-reference.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of method of lattice intercalation induction FOX-7 explosive densification, which comprises the following steps:
Step 1: according to molar ratio be 1:3~1 by high nitrogen two-dimensional polymer monomer and 1,1- diamino -2,2- dinitro ethylene:
10 are added organic solvent, and heating obtains hot solution；
Step 2: organic aldehyde solution being added in hot solution described in step 1, maintains the heating temperature in step 1, while stirring
Reaction 10 minutes~120 minutes, obtains mixed liquor；
Step 3: the anti-solvent isometric with solvent, which is added, into the mixed liquor that step 2 obtains is precipitated product；Obtained product
After centrifugation and drying, high density FOX-7 based composites are obtained.
2. a kind of method of lattice intercalation induction FOX-7 explosive densification according to claim 1, which is characterized in that
In the step 1, the high nitrogen two-dimensional polymer monomer is triaminoguanidine hydrochloride or triaminoguanidinium nitrate.
3. a kind of method of lattice intercalation induction FOX-7 explosive densification according to claim 1, which is characterized in that
In the step 1, the total concentration range of the high nitrogen two dimension and FOX-7 are 50mg/mL~150mg/mL.
4. a kind of method of lattice intercalation induction FOX-7 explosive densification according to claim 1, which is characterized in that
In the step 1, the organic solvent is dimethyl sulfoxide, N, N- dimethyl imide or thionyl chloride, the heating temperature
It is 70 DEG C~110 DEG C.
5. a kind of method of lattice intercalation induction FOX-7 explosive densification according to claim 1, which is characterized in that
In the step 2, the organic aldehyde solution is formaldehyde, acetaldehyde or the glyoxal of mass fraction 37%.
6. a kind of method of lattice intercalation induction FOX-7 explosive densification according to claim 1, which is characterized in that
In the step 2, the molar ratio of high nitrogen two-dimensional polymer monomer and organic aldehyde is 1:2.
7. a kind of method of lattice intercalation induction FOX-7 explosive densification according to claim 1, which is characterized in that
In the step 2, stirring rate is 100rpm~1000rpm.
8. a kind of method of lattice intercalation induction FOX-7 explosive densification according to claim 1, which is characterized in that
In the step 3, the anti-solvent is deionized water, methanol or ethyl alcohol, and dosage is and the bodies such as organic solvent in step 1
Product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910712383.8A CN110372460A (en) | 2019-08-02 | 2019-08-02 | A kind of method of lattice intercalation induction FOX-7 explosive densification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910712383.8A CN110372460A (en) | 2019-08-02 | 2019-08-02 | A kind of method of lattice intercalation induction FOX-7 explosive densification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110372460A true CN110372460A (en) | 2019-10-25 |
Family
ID=68257843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910712383.8A Pending CN110372460A (en) | 2019-08-02 | 2019-08-02 | A kind of method of lattice intercalation induction FOX-7 explosive densification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110372460A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424339A (en) * | 2018-03-23 | 2018-08-21 | 西北工业大学 | A kind of preparation method of high nitrogen two dimension conjugated structure doping vario-property nitrolite crystal |
| CN111908990A (en) * | 2020-07-17 | 2020-11-10 | 中北大学 | Energetic material filled layered framework composite structure and preparation method thereof |
| CN114436720A (en) * | 2022-02-21 | 2022-05-06 | 南京理工大学 | High-energy insensitive coated explosive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4431468A (en) * | 1980-05-21 | 1984-02-14 | Angus Chemical Company | TL-170 Blasting agent |
| CN108424339A (en) * | 2018-03-23 | 2018-08-21 | 西北工业大学 | A kind of preparation method of high nitrogen two dimension conjugated structure doping vario-property nitrolite crystal |
| CN109678632A (en) * | 2019-01-29 | 2019-04-26 | 中北大学 | A kind of two dimension energetic material and preparation method thereof |
-
2019
- 2019-08-02 CN CN201910712383.8A patent/CN110372460A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4431468A (en) * | 1980-05-21 | 1984-02-14 | Angus Chemical Company | TL-170 Blasting agent |
| CN108424339A (en) * | 2018-03-23 | 2018-08-21 | 西北工业大学 | A kind of preparation method of high nitrogen two dimension conjugated structure doping vario-property nitrolite crystal |
| CN109678632A (en) * | 2019-01-29 | 2019-04-26 | 中北大学 | A kind of two dimension energetic material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424339A (en) * | 2018-03-23 | 2018-08-21 | 西北工业大学 | A kind of preparation method of high nitrogen two dimension conjugated structure doping vario-property nitrolite crystal |
| CN108424339B (en) * | 2018-03-23 | 2020-07-14 | 西北工业大学 | Preparation method of high-nitrogen two-dimensional conjugated structure doped modified ammonium nitrate explosive crystal |
| CN111908990A (en) * | 2020-07-17 | 2020-11-10 | 中北大学 | Energetic material filled layered framework composite structure and preparation method thereof |
| CN111908990B (en) * | 2020-07-17 | 2021-07-09 | 中北大学 | Energetic material filled layered framework composite structure and preparation method thereof |
| CN114436720A (en) * | 2022-02-21 | 2022-05-06 | 南京理工大学 | High-energy insensitive coated explosive and preparation method thereof |
| CN114436720B (en) * | 2022-02-21 | 2022-08-26 | 南京理工大学 | High-energy insensitive coated explosive and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110372460A (en) | A kind of method of lattice intercalation induction FOX-7 explosive densification | |
| Singh et al. | Synthesis, characterization and evaluation of polyacrylamide graft starch/clay nanocomposite hydrogel system for enhanced oil recovery | |
| Finckh et al. | The polymerization behavior of [1]-and [2] ferrocenophanes containing silicon atoms in the bridge: comparison of the molecular structure of the strained, polymerizable cyclic ferrocenylsilane Fe (. eta.-C5H4) 2 (SiMe2) with that of the cyclic ferrocenyldisilane Fe (. eta.-C5H4) 2 (SiMe2) 2 | |
| He et al. | Tetraphenylethene-functionalized conjugated helical poly (phenyl isocyanide) with tunable light emission, assembly morphology, and specific applications | |
| Michinobu et al. | One-step synthesis of donor-acceptor type conjugated polymers from ferrocene-containing poly (aryleneethynylene) s | |
| Li et al. | Ferrocene-based poly (aroxycarbonyltriazole) s: synthesis by metal-free click polymerization and use as precursors to magnetic ceramics | |
| Liu et al. | Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid, Photoresponsive, Nanoscale, Building Blocks | |
| CN104673275B (en) | A kind of activation luminescent material and preparation method thereof | |
| Rodriguez et al. | Polyampholyte polymer as a stabiliser for subgrade soil | |
| Xu et al. | A facile synthetic route to multifunctional poly (3-hexylthiophene)-b-poly (phenyl isocyanide) copolymers: from aggregation-induced emission to controlled helicity | |
| Yu et al. | Well‐Defined Magnetic Responsive Polymers Containing Ammonium FeCl4 from ROMP | |
| Maust et al. | Controlled polymerization of norbornene cycloparaphenylenes expands carbon nanomaterials design space | |
| CN113861340A (en) | Application of novel deep profile control and flooding gel | |
| Shi et al. | Nonisothermal cure kinetics in the synthesis of polybenzoxazine–clay nanocomposites | |
| Ikeda et al. | Rhodium-Catalyzed stitching polymerization of alkynylsilylacetylenes | |
| CN107552807A (en) | It is a kind of to prepare the preparation method with the size gold nanorods controllable with dispersiveness on a large scale | |
| Yang et al. | Laboratory evaluation of a controllable self-degradable temporary plugging agent in fractured reservoir | |
| Shi et al. | Investigation of isothermal curing behaviour during the synthesis of polybenzoxazine-layered silicate nanocomposites via cyclic monomer | |
| Abe et al. | Fabrication of double-stranded vinyl polymers mediated by coordination nanochannels | |
| Sepehrianazar et al. | Synthesis and characterization of (allylamine hydrochloride-vinyl sulfonic acid) copolymer and determination of monomer reactivity ratios | |
| Yu et al. | Anchoring effect of hyperbranched carborane in highly cross-linked cyclosiloxane networks toward high-performance polymers | |
| Feuerstein et al. | Polycobaltoceniumylmethylene–A Water-Soluble Polyelectrolyte Prepared by Ring-Opening Transmetalation Polymerization | |
| Köstler et al. | Amphiphilic block copolymers containing thermally degradable poly (phthalaldehyde) blocks | |
| Nietzel et al. | Organic nanoparticles as fragmentable support for Z iegler–N atta catalysts | |
| Dou et al. | Synthesis of Highly Stable and Reactive Nitrile N-Oxides and Their Application as Catalyst-Free Crosslinkers |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191025 |
|
| RJ01 | Rejection of invention patent application after publication |