CN105906847A - Environment-friendly nano hollow plate and preparation method thereof - Google Patents
Environment-friendly nano hollow plate and preparation method thereof Download PDFInfo
- Publication number
- CN105906847A CN105906847A CN201610261504.8A CN201610261504A CN105906847A CN 105906847 A CN105906847 A CN 105906847A CN 201610261504 A CN201610261504 A CN 201610261504A CN 105906847 A CN105906847 A CN 105906847A
- Authority
- CN
- China
- Prior art keywords
- parts
- environment
- board material
- hollow board
- nano hollow
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an environment-friendly nano hollow plate and a preparation method thereof; the environment-friendly nano hollow plate comprises the following components in parts by weight: 19-42 parts of a carbon fiber, 12-33 parts of a konjac sol, 13-32 parts of nano titanium dioxide, 12-25 parts of polyethylene plastic particles, 13-26 parts of nano silver oxide particles, 8-17 parts of acrylic resin, 18-34 parts of dialdehyde starch, 9-24 parts of a glass fiber, 9-21 parts of glycerol, 18-38 parts of ethanol, 13-21 parts of sodium acetate, and 22-44 parts of water. The environment-friendly nano hollow plate has the beneficial effects: (1) the prepared environment-friendly nano hollow plate is easy to degrade, and cannot cause secondary pollution to the environment; and (2) the prepared environment-friendly nano hollow plate has the advantages of good wear resistance and better anti-cracking properties.
Description
Technical field
The invention belongs to packaging material field, relate to hollow board material packaging material, particularly relate to a kind of environment-protection nano hollow board material and
Its preparation method.
Background technology
Nano material is the new material just grown up the eighties in 20th century, and many scientists think that it is 21 century most to have development
One of new material of future.Skin effect that nano material causes because of its quantum size, quantum size effect, small-size effect,
The special effectses such as macroscopic quantum orbital effect, thus have optical effect, high conductivity and diffusibility, high specific heat and the heat of uniqueness
Expansion, high susceptibility and coercivity, also show that and macroscopic view crystalline material at aspects such as catalysis, Optical Electro-Chemistry, fusing point, superconductions
Different characteristics, has the most potential application in each field.At present, nanotechnology main direction of studying in the food industry
Have: nano-packaging, nanometer spray the food such as continue thin film, nanoscale composite or nano composite plastics, nano-antibacterial insurance plastic sheeting
The research of product packaging material.
Along with improving constantly of people's living standard, increasingly stronger, so the packaging material of food are to the safety consciousness of food
Cover all of field of food, and after such packaging material abandoned, can be with long-term existence in certainly due to the strongest stability
So in environment, one of important polluter causing people's productive life.The recovering means generally used is to bury or burn, so
Not only consume the energy, and cause secondary pollution to environment.
In recent years, people are while researching and solving Recycle of Waste Plastics, and degradation plastic also becomes global one
Individual study hotspot, degradation plastic is broadly divided into photodegradation plastics and biodegradable plastic.And utilize the effect of microorganism
Lower meeting is degraded automatically, is finally converted into carbon dioxide and water under Soil Microorganism metabolism, will not cause environment pollution.
But the performances such as above-mentioned nano material of the prior art or ep-type material are when for packaging material, wear-resistant rate are relatively
Difference.
Summary of the invention
Present invention solves the technical problem that: in order to overcome the defect of above-mentioned prior art, it is thus achieved that one is prone to degraded, will not be to ring
Secondary pollution is caused in border, and has the hollow board material of superperformance, the invention provides a kind of environment-protection nano hollow board material and system thereof
Preparation Method.
Technical scheme: a kind of environment-protection nano hollow board material, is made up of following components proportioning by weight: carbon fiber 19～42 parts,
Konjac sol 12～33 parts, nano titanium oxide 13～32 parts, vinyon particle 12～25 parts, nano oxidized Argent grain 13～26
Part, acrylic resin 8～17 parts, dialdehyde starch 18～34 parts, glass fibre 9～24 parts, glycerol 9～21 parts, ethanol 18～38
Part, sodium acetate 13～21 parts, water 22～44 parts.
Preferably, it is made up of following components proportioning by weight: 36 parts of carbon fiber, konjac sol 27 parts, nanometer titanium dioxide
Titanium 26 parts, 21 parts of vinyon particle, nano oxidized Argent grain 19 parts, acrylic resin 13 parts, dialdehyde starch 32 parts,
Glass fibre 19 parts, glycerol 17 parts, ethanol 33 parts, sodium acetate 16 parts, 40 parts of water.
The preparation method of a kind of environment-protection nano hollow board material, comprises the steps of
(1) konjac sol, dialdehyde starch, acrylic resin and glycerol are added to the water, are 78 DEG C～102 DEG C, pH in temperature
Value is the prepared pasty state that stirs under conditions of 6.7～7.3；Pasty mixture is added in autoclave, 2.2～4.8MPa
Under the conditions of react 35～50 minutes；
(2) carbon fiber, nano titanium oxide, vinyon particle, nano oxidized Argent grain and glass fibre are added ethanol
In, it is placed in autoclave, reacts 30～65 minutes under 288 DEG C～390 DEG C of air-proof conditions；
(3) sodium acetate is soluble in water, be placed in the head tank of autoclave, the temperature of head tank be maintained 38 DEG C～
56℃；The mixture that step (1) and step (2) obtain is simultaneously introduced in reactor, and the temperature of reactor maintains 298 DEG C
～405 DEG C, the mixture in dropping head tank, dropping limit, limit is stirred, within 2～4 hours, is dripped off, by temperature of reaction kettle after completion of dropwise addition
It is down to 155 DEG C, and is incubated 35 minutes, prepare environment-protection nano hollow board material precursor material；
(4) the environment-protection nano hollow board material precursor material that step (3) prepares is placed in corotating twin-screw equipment,
Extrude, shape and cut under the conditions of 55 DEG C～90 DEG C and can be prepared by environment-protection nano hollow board material.
Preferably, konjac sol, dialdehyde starch, acrylic resin and glycerol are added to the water in (1) by step, in temperature are
92 DEG C, pH value be the prepared pasty state that stirs under conditions of 7.1；Pasty mixture is added in autoclave, at 4.1MPa
Under the conditions of react 43 minutes.
Preferably, by carbon fiber, nano titanium oxide, vinyon particle, nano oxidized Argent grain and glass in step (2)
Glass fiber adds in ethanol, is placed in autoclave, reacts 56 minutes under 365 DEG C of air-proof conditions.
Preferably, in step (3), sodium acetate is soluble in water, it is placed in the head tank of autoclave, the temperature of head tank
It is maintained 48 DEG C；The mixture that step (1) and step (2) obtain is simultaneously introduced in reactor, and the temperature dimension of reactor
Holding at 368 DEG C, the mixture in dropping head tank, dropping limit, limit is stirred, within 3 hours, is dripped off, by temperature of reaction kettle after completion of dropwise addition
It is down to 155 DEG C, and is incubated 35 minutes, prepare environment-protection nano hollow board material precursor material.
Preferably, the environment-protection nano hollow board material precursor material that step (3) prepares is placed in cocurrent and parallel by step (4)
In twin screw device, extrude, shape and cut under the conditions of 78 DEG C and can be prepared by environment-protection nano hollow board material.
Beneficial effect: the environment-protection nano hollow board material that (1) present invention prepares is prone to degraded, will not cause secondary dirty to environment
Dye；(2) the environment-protection nano hollow board material anti-wear performance that the present invention prepares is good, and cracking resistance is preferable.
Detailed description of the invention
Embodiment 1
A kind of environment-protection nano hollow board material, is made up of following components proportioning by weight: 19 parts of carbon fiber, konjac sol 12
Part, nano titanium oxide 13 parts, 12 parts of vinyon particle, nano oxidized Argent grain 13 parts, acrylic resin 8 parts,
Dialdehyde starch 18 parts, glass fibre 9 parts, glycerol 9 parts, ethanol 18 parts, sodium acetate 13 parts, 22 parts of water.
The preparation method of a kind of environment-protection nano hollow board material, comprises the steps of
(1) konjac sol, dialdehyde starch, acrylic resin and glycerol are added to the water, temperature be 78 DEG C, pH value be 6.7
Under conditions of stir prepared pasty state；Pasty mixture is added in autoclave, under the conditions of 2.2MPa, react 35 points
Clock；
(2) carbon fiber, nano titanium oxide, vinyon particle, nano oxidized Argent grain and glass fibre are added ethanol
In, it is placed in autoclave, reacts 30 minutes under 288 DEG C of air-proof conditions；
(3) sodium acetate is soluble in water, it is placed in the head tank of autoclave, the temperature of head tank is maintained 38 DEG C；
The mixture that step (1) and step (2) obtain is simultaneously introduced in reactor, and the temperature of reactor maintains 298 DEG C,
Mixture in dropping head tank, the stirring of dropping limit, limit, within 2 hours, drip off, after completion of dropwise addition, temperature of reaction kettle is down to 155 DEG C,
And it is incubated 35 minutes, prepare environment-protection nano hollow board material precursor material；
(4) the environment-protection nano hollow board material precursor material that step (3) prepares is placed in corotating twin-screw equipment,
Extrude, shape and cut under the conditions of 55 DEG C and can be prepared by environment-protection nano hollow board material.
Embodiment 2
A kind of environment-protection nano hollow board material, is made up of following components proportioning by weight: 36 parts of carbon fiber, konjac sol 27
Part, nano titanium oxide 26 parts, 21 parts of vinyon particle, nano oxidized Argent grain 19 parts, acrylic resin 13 parts,
Dialdehyde starch 32 parts, glass fibre 19 parts, glycerol 17 parts, ethanol 33 parts, sodium acetate 16 parts, 40 parts of water.
The preparation method of a kind of environment-protection nano hollow board material, comprises the steps of
(1) konjac sol, dialdehyde starch, acrylic resin and glycerol are added to the water, temperature be 92 DEG C, pH value be 7.1
Under conditions of stir prepared pasty state；Pasty mixture is added in autoclave, under the conditions of 4.1MPa, react 43 points
Clock；
(2) carbon fiber, nano titanium oxide, vinyon particle, nano oxidized Argent grain and glass fibre are added ethanol
In, it is placed in autoclave, reacts 56 minutes under 365 DEG C of air-proof conditions；
(3) sodium acetate is soluble in water, it is placed in the head tank of autoclave, the temperature of head tank is maintained 48 DEG C；
The mixture that step (1) and step (2) obtain is simultaneously introduced in reactor, and the temperature of reactor maintains 368 DEG C,
Mixture in dropping head tank, the stirring of dropping limit, limit, within 3 hours, drip off, after completion of dropwise addition, temperature of reaction kettle is down to 155 DEG C,
And it is incubated 35 minutes, prepare environment-protection nano hollow board material precursor material；
(4) the environment-protection nano hollow board material precursor material that step (3) prepares is placed in corotating twin-screw equipment,
Extrude, shape and cut under the conditions of 78 DEG C and can be prepared by environment-protection nano hollow board material.
Embodiment 3
A kind of environment-protection nano hollow board material, is made up of following components proportioning by weight: 42 parts of carbon fiber, konjac sol 33
Part, nano titanium oxide 32 parts, 25 parts of vinyon particle, nano oxidized Argent grain 26 parts, acrylic resin 17 parts,
Dialdehyde starch 34 parts, glass fibre 24 parts, glycerol 21 parts, ethanol 38 parts, sodium acetate 21 parts, 44 parts of water.
The preparation method of a kind of environment-protection nano hollow board material, comprises the steps of
(1) konjac sol, dialdehyde starch, acrylic resin and glycerol are added to the water, temperature be 102 DEG C, pH value be
Stir under conditions of 7.3 prepared pasty state；Pasty mixture is added in autoclave, under the conditions of 4.8MPa, react 50
Minute；
(2) carbon fiber, nano titanium oxide, vinyon particle, nano oxidized Argent grain and glass fibre are added ethanol
In, it is placed in autoclave, reacts 65 minutes under 390 DEG C of air-proof conditions；
(3) sodium acetate is soluble in water, it is placed in the head tank of autoclave, the temperature of head tank is maintained 56 DEG C；
The mixture that step (1) and step (2) obtain is simultaneously introduced in reactor, and the temperature of reactor maintains 405 DEG C,
Mixture in dropping head tank, the stirring of dropping limit, limit, within 4 hours, drip off, after completion of dropwise addition, temperature of reaction kettle is down to 155 DEG C,
And it is incubated 35 minutes, prepare environment-protection nano hollow board material precursor material；
(4) the environment-protection nano hollow board material precursor material that step (3) prepares is placed in corotating twin-screw equipment,
Extrude, shape and cut under the conditions of 90 DEG C and can be prepared by environment-protection nano hollow board material.
The environment-protection nano hollow board material preparing above-described embodiment 1～3 detects, and result is as shown in table 1:
The environment-protection nano hollow board material testing result that table 1 embodiment 1～3 prepares
Claims (7)
1. an environment-protection nano hollow board material, it is characterised in that be made up of following components proportioning by weight: carbon fiber 19～42
Part, konjac sol 12～33 parts, nano titanium oxide 13～32 parts, vinyon particle 12～25 parts, nano phase ag_2 o
Granule 13～26 parts, acrylic resin 8～17 parts, dialdehyde starch 18～34 parts, glass fibre 9～24 parts, glycerol 9～21
Part, ethanol 18～38 parts, sodium acetate 13～21 parts, water 22～44 parts.
A kind of environment-protection nano hollow board material the most according to claim 1, it is characterised in that by following components proportioning by weight
Composition: 36 parts of carbon fiber, konjac sol 27 parts, nano titanium oxide 26 parts, 21 parts of vinyon particle, nanometer
Silver oxide particle 19 parts, acrylic resin 13 parts, dialdehyde starch 32 parts, glass fibre 19 parts, glycerol 17 parts, second
Alcohol 33 parts, sodium acetate 16 parts, 40 parts of water.
3. the preparation method of a kind of environment-protection nano hollow board material described in claim 1, it is characterised in that comprise the steps of
(1) konjac sol, dialdehyde starch, acrylic resin and glycerol are added to the water, are 78 DEG C～102 DEG C, pH in temperature
Value is the prepared pasty state that stirs under conditions of 6.7～7.3；Pasty mixture is added in autoclave, 2.2～4.8MPa
Under the conditions of react 35～50 minutes；
(2) carbon fiber, nano titanium oxide, vinyon particle, nano oxidized Argent grain and glass fibre are added ethanol
In, it is placed in autoclave, reacts 30～65 minutes under 288 DEG C～390 DEG C of air-proof conditions；
(3) sodium acetate is soluble in water, be placed in the head tank of autoclave, the temperature of head tank be maintained 38 DEG C～
56℃；The mixture that step (1) and step (2) obtain is simultaneously introduced in reactor, and the temperature of reactor maintains 298 DEG C
～405 DEG C, the mixture in dropping head tank, dropping limit, limit is stirred, within 2～4 hours, is dripped off, by temperature of reaction kettle after completion of dropwise addition
It is down to 155 DEG C, and is incubated 35 minutes, prepare environment-protection nano hollow board material precursor material；
(4) the environment-protection nano hollow board material precursor material that step (3) prepares is placed in corotating twin-screw equipment,
Extrude, shape and cut under the conditions of 55 DEG C～90 DEG C and can be prepared by environment-protection nano hollow board material.
The preparation method of a kind of environment-protection nano hollow board material the most according to claim 3, it is characterised in that will in step (1)
Konjac sol, dialdehyde starch, acrylic resin and glycerol are added to the water, temperature be 92 DEG C, pH value be the condition of 7.1
Under stir prepared pasty state；Pasty mixture is added in autoclave, react 43 minutes under the conditions of 4.1MPa.
The preparation method of a kind of environment-protection nano hollow board material the most according to claim 3, it is characterised in that will in step (2)
Carbon fiber, nano titanium oxide, vinyon particle, nano oxidized Argent grain and glass fibre add in ethanol, juxtaposition
In autoclave, react 56 minutes under 365 DEG C of air-proof conditions.
The preparation method of a kind of environment-protection nano hollow board material the most according to claim 3, it is characterised in that will in step (3)
Sodium acetate is soluble in water, is placed in the head tank of autoclave, and the temperature of head tank is maintained 48 DEG C；By step (1)
The mixture obtained with step (2) is simultaneously introduced in reactor, and the temperature of reactor maintains 368 DEG C, a dropping high position
Mixture in groove, dropping limit, limit is stirred, within 3 hours, is dripped off, after completion of dropwise addition, temperature of reaction kettle is down to 155 DEG C, and protects
Temperature 35 minutes, prepares environment-protection nano hollow board material precursor material.
The preparation method of a kind of environment-protection nano hollow board material the most according to claim 3, it is characterised in that will in step (4)
The environment-protection nano hollow board material precursor material that step (3) prepares is placed in corotating twin-screw equipment, at 78 DEG C of bars
Extrude, shape and cut under part and can be prepared by environment-protection nano hollow board material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610261504.8A CN105906847A (en) | 2016-04-25 | 2016-04-25 | Environment-friendly nano hollow plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610261504.8A CN105906847A (en) | 2016-04-25 | 2016-04-25 | Environment-friendly nano hollow plate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105906847A true CN105906847A (en) | 2016-08-31 |
Family
ID=56752830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610261504.8A Pending CN105906847A (en) | 2016-04-25 | 2016-04-25 | Environment-friendly nano hollow plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105906847A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353445A (en) * | 2017-08-21 | 2017-11-17 | 安徽省天乐塑业有限公司 | Fully-degradable food packing material is blended in a kind of carbon fiber novolac epoxy resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766277A (en) * | 2012-08-01 | 2012-11-07 | 江西禾尔斯环保科技有限公司 | Plant fiber composite micro-foaming biodegradable hollow plates |
| CN103834095A (en) * | 2012-11-21 | 2014-06-04 | 辽宁辽杰科技有限公司 | Hollow plate and manufacturing method thereof |
| CN104861283A (en) * | 2015-03-31 | 2015-08-26 | 苏州市鼎立包装有限公司 | Impact-resistant modified plastic hollow plate and preparation method thereof |
-
2016
- 2016-04-25 CN CN201610261504.8A patent/CN105906847A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766277A (en) * | 2012-08-01 | 2012-11-07 | 江西禾尔斯环保科技有限公司 | Plant fiber composite micro-foaming biodegradable hollow plates |
| CN103834095A (en) * | 2012-11-21 | 2014-06-04 | 辽宁辽杰科技有限公司 | Hollow plate and manufacturing method thereof |
| CN104861283A (en) * | 2015-03-31 | 2015-08-26 | 苏州市鼎立包装有限公司 | Impact-resistant modified plastic hollow plate and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353445A (en) * | 2017-08-21 | 2017-11-17 | 安徽省天乐塑业有限公司 | Fully-degradable food packing material is blended in a kind of carbon fiber novolac epoxy resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104192910B (en) | A kind of preparation method of wolframic acid caesium nano-powder | |
| CN100463860C (en) | Method for preparing stannic oxide hollow sphere | |
| CN103101924B (en) | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method | |
| CN106220996A (en) | The preparation method of silicon white carbon black/composite polyolefine material | |
| CN104845301A (en) | Ultraviolet screening agent, preparation method thereof, polylactic acid film containing ultraviolet screening agent and preparation method of polylactic acid film | |
| CN102294239B (en) | Metal nano electro-catalyst for redox reaction of fuel cell, and preparation method and application thereof | |
| CN107349938A (en) | A kind of nickel sulfide cadmium sulfide nano wires heterojunction structure and preparation method thereof | |
| CN107188232A (en) | A kind of petal-shaped tungsten sulfide nanosphere, preparation method and applications | |
| CN101987898A (en) | Special modified superfine coal powder masterbatch for drip irrigation tape | |
| CN105906847A (en) | Environment-friendly nano hollow plate and preparation method thereof | |
| CN106994356A (en) | The preparation method of photochemical catalyst CdS NiS nano composite materials | |
| CN109046450A (en) | A kind of BiOCl/(BiO)2CO3The cellulose acetate of load/fibroin hybridized film preparation method and application | |
| CN106807399A (en) | Selective deposition has the preparation method of the titanium deoxide catalyst of Mock gold particle | |
| CN112237839B (en) | Construction method and application of transition metal mediated semi-artificial photosynthesis system | |
| CN103695850B (en) | The preparation method of solar cell CIGS target | |
| CN102194532A (en) | Preparation method of compound powder of boron carbide and carbon | |
| Bhuyan et al. | Advances in nanotechnology for biofuel production | |
| CN106098915A (en) | A kind of nano-perovskite modified silica-gel being applied to LED plant growth lamp chip package | |
| CN104497426A (en) | Tackifying master batch and preparation method thereof | |
| CN110142838A (en) | A kind of preparation method of the phase-change accumulation energy timber of carbon covered metal filler | |
| CN110343283B (en) | Preparation method of photocatalyst device with skeleton of tin dioxide/tin tungstate printed in 3D mode | |
| CN109261191B (en) | Graphite phase carbon nitride foam photocatalytic material and preparation method thereof | |
| CN108922785B (en) | Preparation method of counter electrode material of dye-sensitized solar cell | |
| CN104495762B (en) | Nanocrystalline ZnSe preparation method, ZnSe be nanocrystalline and the preparation method of ZnSe cushions | |
| CN114276600B (en) | Preparation method of degradable PE film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160831 |
|
| RJ01 | Rejection of invention patent application after publication |