CN1660939A - Anticorrosive heat retaining rigid foam of asphaltum polyurethane modified by polyether glycol of organic aminated substance - Google Patents
Anticorrosive heat retaining rigid foam of asphaltum polyurethane modified by polyether glycol of organic aminated substance Download PDFInfo
- Publication number
- CN1660939A CN1660939A CN 200510042401 CN200510042401A CN1660939A CN 1660939 A CN1660939 A CN 1660939A CN 200510042401 CN200510042401 CN 200510042401 CN 200510042401 A CN200510042401 A CN 200510042401A CN 1660939 A CN1660939 A CN 1660939A
- Authority
- CN
- China
- Prior art keywords
- polyether glycol
- component
- foamed polyurethane
- hard foamed
- asphalt
- 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
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
A polyester polyol modified hard foam asphalt polyurethane material with anticorrosion and insulating functions is prepared through preparing component A from polyether polyol, coal asphalt liquid, organosilicon as foam stabilizer, cross-linking agent, composite catalyst, foaming agent and flame-retarder, proportionally mixing it with polyisocyanate, and chemical foaming.
Description
Technical field
The present invention relates to a kind of novel steel pipeline anti-corrision thermal insulation, the waterproof thermal-insulated hard foam material of using of roofing and wall.It specifically is the asphalt hard foamed polyurethane of modified by polyether glycol of organic aminated substance.
Background technology
The rigid polyurethane foam has insulation cold insulation heat-insulating property, and asphalt hard foamed polyurethane has bituminous waterproof, protection against corrosion again concurrently and resists atmospheric weathering.Paper " A novel asphalt-blended polyurethane foam " in the U.S. association of plastics industry annual meeting proceedings in 1989 has reported that blending bituminous urethane foam is used for automotive industry sound insulation vibration damping waterproof sealing adiabatic elasticity foam-body material.
U.S. chemical abstract CA 114,248806 has reported the polyester modification coal-tar pitch that makes hydroxyl with the thermal destruction in coal-tar pitch of polyethylene terephthalate waste, is used to prepare elastic polyurethane fine-celled foam sealing material.
Chinese patent 01127528.6 is used for the casting type asphalt hard foamed polyurethane, Chinese patent 03139180.x, the asphalt hard foamed polyurethane that is used to spray.Yet the asphalt polyurethane hard bubble composite material is because thickening and gelatin phenomenon can appear in the bituminous existence.
One of purpose of the present invention is synthetic a kind of and polyether glycol of organic aminated substance with avidity compatible with coal-tar pitch, in order to modified coal pitch, overcome thickening and the gelatin phenomenon of coal-tar pitch in polyurethane hard bubble composite material, improve the package stability of asphalt polyurethane hard bubble composite material.
Two of purpose of the present invention is preparation mix type polyisocyanate curing agents.
Three of purpose of the present invention is to utilize the asphalt polyurethane combination material and mix type polyisocyanate curing agent of modification, prepares asphalt hard foamed polyurethane through chemical foaming.It is good that this hard foam has the feel snappiness, overcome that the foams that cause because of pitch are crisp, the defective of contraction, rebound resilience difference; And can keep hard foam thermal conductivity and mechanical property unaffected.
Summary of the invention
Task of the present invention is realized by following technical proposal:
At first synthetic polyether glycol of organic aminated substance; Refabrication tolylene diisocyanate polyethers performed polymer and many phenyl polymethine polyisocyanates mix type polyisocyanate curing agent; With cold cut preparation coal-tar pitch liquid, and preparation asphalt polyurethane hard bubble composite material; Utilize this combination material to carry out chemical foaming and prepare asphalt hard foamed polyurethane with the mix type polyisocyanate curing agent.
The preparation of asphalt hard foamed polyurethane of the present invention be with the polyether glycol of organic aminated substance blending in coal-tar pitch liquid, cooperate silicon foams stablizer, linking agent, composite catalyst, whipping agent, fire retardant to be mixed with asphalt polyurethane hard bubble composite material A component again.The mixed chemical foaming by a certain percentage of the mix type polyisocyanates B component of combination material A component and the present invention's preparation makes asphalt hard foamed polyurethane.This asphalt hard foamed polyurethane chemical constitution is:
Asphalt hard foamed polyurethane combination material A component:
Raw materials quality part
Coal-tar pitch liquid 100
Polyether glycol of organic aminated substance 80-120
Linking agent 10-20
Silicon foams stablizer 6-8
Composite catalyst 12-24
Cocatalyst 1.5-9.8
Fire retardant 0-60
Water foaming agent 0.5-1.5
HCFC-141B whipping agent 70-90
The B component: mix type polyisocyanate curing agent, its isocyanate index are 1.05-1.10.
The polyether glycol of organic aminated substance that is adopted in the aforesaid combination material A component can be urea polyether glycol, quadrol polyether glycol, diethylenetriamine polyether glycol, trolamine polyether glycol and tolylene diamine polyether glycol, and they are to be the polyether glycol of organic aminated substance that initiator and propylene oxide ring-opening polymerization make with the organic aminated substance.Its preparation technology is:
At first in the stainless steel pressure reactor, drop into the organic amine initiator, with closed reactor behind the air in the nitrogen replacement reactor, be warming up to 70-80 ℃, under agitation drop into propylene oxide in batches, polymeric reaction temperature is controlled at 100-115 ℃, polymerization pressure is controlled at 0.3-0.4Mpa, after treating that required propylene oxide all adds, pressure is reduced near zero the time in the reactor, inflated with nitrogen 0.2-0.3Mpa continues reaction 1 hour, opens vacuum pump and removes unreacted monomer and moisture, sampling analysis filters discharging.
Usually the two is composite to adopt urea polyether glycol and quadrol polyether glycol.The urea polyether glycol is to be initiator with the industrial urea, in the presence of solubility promoter, make urea polyoxytrimethylene ether with the propylene oxide ring-opening polymerization, hydroxyl value 550-750KOHmg/g, viscosity 600-1800mpa.s/25 ℃, preferably adopt hydroxyl value 700 ± 30KOHmg/g, viscosity 1000 ± 200mpa.s/25 ℃ urea polyether glycol.Usually consumption is the 40-60 mass parts in prescription.
The quadrol polyether glycol is to be the quadrol polyoxytrimethylene ether that initiator and propylene oxide ring-opening polymerization make with the quadrol, and hydroxyl value is 770 ± 35KOHmg/g, and viscosity 3500-5500mpa.s/25 ℃, consumption is the 60-40 mass parts usually.
The preparation technology of the coal-tar pitch liquid that is adopted in the aforesaid combination material A component:
In reactor, at first drop into aromatic solvent, open and stir, be warming up to 80-90 ℃, drop into the coal-tar pitch that is broken into fritter in advance in batches.Coal-tar pitch should slowly add in batches, in case the excessive bonding of viscosity stirs.After pitch adds, closed reactor, stirring is dissolved pitch fully under 80-95 ℃, and solvent pitch is removed by filter impurity with whizzer, puts into basin and staticizes standby.
The composite catalyst that is adopted in the aforesaid combination material A component is usually by tertiary amine, 31 (dimethyl aminomethyl) phenol for example, triethylene diamine and organo-metallic carboxylate salt, for example Potassium ethanoate, potassium oleate, potassium octanoate is composite forms optimum amount 16-18 mass parts.
The cocatalyst that is adopted in the aforesaid combination material A component adopts N.N-dimethylcyclohexylamine and dibutyl tin laurate usually.The optimum amount 1.5-8.0 mass parts of N.N-dimethylcyclohexylamine, the optimum amount 0.8-1.6 mass parts of dibutyl tin laurate.
The whipping agent that is adopted in the aforesaid combination material A component is: HCFC-141B (a fluorine ethylene dichloride), HFC-245fa (pentafluoropropane), water (emitting carbonic acid gas with the polyisocyanates reaction).Usually adopt water and other whipping agent to be used, form the common foaming system of carbonic acid gas and other whipping agent.
The fire retardant that is adopted in the aforesaid combination material A component adopts liquid additive flame retardant usually, for example, and trichloroethyl phosphate (TCEP), trichlorine propyl phosphate (TCPP), tribromo propyl phosphate, methyl-phosphoric acid dimethyl ester (DMMP) etc.Fire retardant preferably both or three is composite, and the present invention selects for use trichloroethyl phosphate (TCEP) and methyl-phosphoric acid dimethyl ester (DMMP) composite, and consumption is the 40-60 mass parts usually.
The suds-stabilizing agent that is adopted in the aforesaid combination material A component is non-hydrolysis-type silicon-carbon bond silicon foams stablizer, and the present invention adopts non-hydrolysis-type water soluble polyether siloxanes, common consumption 6-8 part, optimum amount 4-6 mass parts.Linking agent can adopt trolamine, Viscotrol C and Stockholm tar one or both, three kinds composite, with two kinds composite preferable, optimum amount 10-20 mass parts.
The blending process of above-mentioned asphalt hard foamed polyurethane combination material A component is:
At first drop into polyether glycol of organic aminated substance in reactor, open and stir, under agitation drop into silicon foams stablizer, linking agent, coal-tar pitch liquid, catalyzer, fire retardant successively, whipping agent is dropped in the back that stirs.At the uniform velocity stir under the room temperature.Inspection by sampling filters and packages.
Above-mentioned mix type polyisocyanates B component is the performed polymer that tolylene diisocyanate and two functionality propylene glycol polyoxytrimethylene ethers and three-functionality-degree glycerine polyoxytrimethylene ether make, and this performed polymer and many phenyl polymethine polyisocyanates are mixed and made into the mix type polyisocyanates by a certain percentage.Since blending polyether-type tolylene diisocyanate performed polymer, not only improved isocyanate content, and improved the feel snappiness of asphalt hard foamed polyurethane and the rebound resilience of foams.Its preparation method is:
In stainless steel cauldron, drop into tolylene diisocyanate earlier, under agitation drop into polyether glycol and catalyzer dibutyl tin laurate, temperature of reaction is controlled at 80-90 ℃, reaction times 1-2 hour, treat to squeeze into mixing kettle after prepolymerization reaction is finished, mix with many phenyl polymethine polyisocyanates, filter and package.It is 31.5% (m/m) that sampling records isocyano-content, viscosity 210mpa.s/25 ℃.
The present invention is owing to adopted the asphalt polyurethane hard bubble composite material of modified by polyether glycol of organic aminated substance, make pitch shelf-stable in the combination material, overcome bituminous thickening and gelatin phenomenon, cause the asphalt polyurethane hard bubble composite material do not flocculate, not skinning, do not lump, do not precipitate.Owing to adopt tolylene diisocyanate polyether-type performed polymer and many phenyl polymethine polyisocyanates mix type polyisocyanates as asphalt hard foamed polyurethane B component, this component is expected the hard foam that A component chemical foaming makes with combination, improved defectives such as foams are crisp, rebound resilience difference, made asphalt hard foamed polyurethane be more suitable for reaching " tube-in-tube " anticorrosion adiabatic jacket tube and roofing and wall directly sprays the water-proof heat-insulation layer processing requirement in oil field gathering and transportation oil-piping " single stage method ", " two-step approach ".
Hard foam of the present invention is widely used in waterproof thermal-insulated, the oily buried steel pipeline of oil field gathering and transportation, cities and towns central heating directly-buried thermal insulation pipes and the industrial pipeline anticorrosion insulating layer of construction wall and roofing, corrosion-resistant thermal insulation cold insulation fields such as storage tanker, beer fermentation tank.
Embodiment
Open in detail below in conjunction with embodiment to the present invention.
The preparation of embodiment 1 urea polyether glycol
At 2m
3Drop into solubility promoter water in the stainless steel pressure reactor, ethylene glycol, glycol ether or glycerine, choose wherein one or both, open and stir and drop into solid particulate urea 260kg, with closed reactor behind the air in the nitrogen replacement reactor, be warming up to 70-80 ℃, drop into propylene oxide 700-750kg in batches, the control temperature of reaction kettle is 100-115 ℃, reaction pressure is 0.3-0.4Mpa, after treating that required propylene oxide all adds, reactor pressure is reduced near zero the time, inflated with nitrogen 0.2-0.3Mpa, slaking reaction 1 hour, open vacuum pump and remove unreacted monomer and moisture, sampling analysis, hydroxyl value 710KOHmg/g, viscosity 1100mpa.s/25 ℃, pH value 8.
The preparation of embodiment 2 quadrol polyether glycols
At 2m
3Drop into quadrol 200kg in the stainless steel pressure reactor, closed reactor behind the air in the nitrogen replacement reactor is warming up to 70-80 ℃, drops into propylene oxide 800kg in batches, control reaction temperature 100-115kg, reaction pressure 0.3-0.4Mpa, treat that required propylene oxide all adds after, reactor pressure is reduced near zero the time, unreacted monomer of vacuum removal and moisture, sampling analysis, hydroxyl value 765KOHmg/g, viscosity 3900mpa.s/25 ℃.
The preparation of embodiment 3 mix type polyisocyanates.
At 2m
3Drop into tolylene diisocyanate 600kg in the stainless steel cauldron, under agitation drop into glycerine polyoxytrimethylene ether 400kg and dibutyltin dilaurate catalyst 1-2kg, control reaction temperature 80-90 ℃, 1 hour reaction times, after treating that prepolymerization reaction is finished, squeeze into mixing kettle and many phenyl of 1000kg polymethine polyisocyanates mixes, discharging filters and packages.Sampling analysis records isocyano-content 31.5% (m/m), and viscosity 210mpa.s/25 ℃, density 1.235g/cm
3/ 25 ℃.
The preparation of embodiment 4 coal-tar pitch liquid
At 2m
3Drop into aromatic solvent 350kg in the carbon steel reactor, open and stir, be warming up to 80-90 ℃, drop into the coal-tar pitch 650kg that is broken into fritter in advance in batches, pitch adds the back closed reactor, 80-90 ℃ of control temperature in the kettle,, after stirring is dissolved pitch fully, stop to stir, the pitch that has dissolved is removed by filter impurity with whizzer, put into basin and staticize.Sampling analysis, solid content 66.3%, 125 seconds/25 ℃ of viscosity (being coated with 4 glasss), moisture content 0.23%.
Embodiment 5 pipelines are poured into a mould the preparation of anticorrosion heat insulation asphalt rigid polyurethane foam
Raw materials quality part
Coal-tar pitch liquid 100
Urea polyether glycol 50
Quadrol polyether glycol 60
Silicon foams stablizer CGY-3 6.5
Viscotrol C linking agent 10
Trolamine linking agent 6
Composite catalyst 15
N.N-dimethylcyclohexylamine cocatalyst 2.0
Water 1.0
HCFC-141B whipping agent 75
Mix type polyisocyanates B (isocyanate index 1.05-1.10)
Preparation technology by combination material A is mixed with above-mentioned raw materials, will make up material A and mix type polyisocyanates B mixed chemical foaming (is 1.05 proportionings by isocyanate index) again, makes asphalt hard foamed polyurethane.The performance index of hard bubbling: free foaming density 32kg/m
3, compressive strength 172Kpa, water-intake rate (V/V) 1.2%, thermal conductivity, 0.0236w/m.k.
Embodiment 6 roofing and walls spray waterproof thermal-insulated asphalt hard foamed polyurethane
Raw materials quality part
Coal-tar pitch liquid 100
Urea polyether glycol 60
Quadrol polyether glycol 60
Silicon foams stablizer CGY-3 7.0
Trolamine linking agent 8.0
Stockholm tar linking agent 10.0
Composite catalyst 20
Triethylene diamine catalyzer 6
Organotin cocatalyst 1.0
TCEP fire retardant 35
DMMP fire retardant 15
Water 1.3
HCFC-141B whipping agent 85
Mix type polyisocyanates B (isocyanate index 1.05-1.10)
The preparation method is with embodiment 5, and the performance index of hard bubbling are as follows:
Free foaming density 28.6kg/m
3
Ultimate compression strength 126Kpa
Water-intake rate (V/V) 1.1%
Thermal conductivity 0.0241w/m.k
Claims (9)
1. the asphalt hard foamed polyurethane of a modified by polyether glycol of organic aminated substance is characterized in that, is made the consisting of of A component by combination material A component and the mixed chemical foaming by a certain percentage of mix type polyisocyanates B component:
Raw materials quality part
Coal-tar pitch liquid 100
Polyether glycol of organic aminated substance 80-120
Linking agent 10-20
Silicon foams stablizer 6-8
Composite catalyst 12-24
Cocatalyst 1.5-9.8
Fire retardant 0-60
Water foaming agent 0.5-1.5
HCFC-141B whipping agent 70-90
The B component: mix type polyisocyanate curing agent, its isocyanate index are 1.05-1.10;
Described polyether glycol of organic aminated substance is to be the polyether glycol of organic aminated substance that initiator and propylene oxide ring-opening polymerization make with the organic aminated substance.
2. according to the asphalt hard foamed polyurethane of claim 1, it is characterized in that, described polyether glycol of organic aminated substance be following one or more: urea polyether glycol, quadrol polyether glycol, diethylenetriamine polyether glycol, trolamine polyether glycol and tolylene diamine polyether glycol.
3. according to the asphalt hard foamed polyurethane of claim 2, it is characterized in that described polyether glycol of organic aminated substance is that the two is composite for urea polyether glycol and quadrol polyether glycol.
4. according to the asphalt hard foamed polyurethane of claim 1, it is characterized in that the composite catalyst in the described A component is by tertiary amine and the organo-metallic carboxylate salt is composite forms.
5. according to the asphalt hard foamed polyurethane of claim 1, it is characterized in that the cocatalyst in the described A component is N.N-dimethylcyclohexylamine and dibutyl tin laurate.
6. according to the asphalt hard foamed polyurethane of claim 1, it is characterized in that the fire retardant in the described A component adopts liquid additive flame retardant.
7. according to the asphalt hard foamed polyurethane of claim 1, it is characterized in that, the blending process of described A component is: at first drop into polyether glycol of organic aminated substance in reactor, open and stir, under agitation drop into silicon foams stablizer, linking agent, coal-tar pitch liquid, catalyzer, fire retardant successively, drop into whipping agent after stirring, at the uniform velocity stir under the room temperature, inspection by sampling filters and packages.
8. according to the asphalt hard foamed polyurethane of claim 1, it is characterized in that, described B component is the performed polymer that tolylene diisocyanate and two functionality propylene glycol polyoxytrimethylene ethers and three-functionality-degree glycerine polyoxytrimethylene ether make, and this performed polymer and many phenyl polymethine polyisocyanates are mixed and made into the mix type polyisocyanates by a certain percentage.
9. asphalt hard foamed polyurethane according to Claim 8, it is characterized in that, the preparation method of B component is: drop into tolylene diisocyanate in stainless steel cauldron earlier, under agitation drop into polyether glycol and catalyzer dibutyl tin laurate, temperature of reaction is controlled at 80-90 ℃, reaction times 1-2 hour, treat to squeeze into mixing kettle after prepolymerization reaction is finished, mix with many phenyl polymethine polyisocyanates, filter and package, it is 31.5% (m/m) that sampling records isocyano-content, viscosity 210mpa.s/25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510042401 CN1660939A (en) | 2005-01-24 | 2005-01-24 | Anticorrosive heat retaining rigid foam of asphaltum polyurethane modified by polyether glycol of organic aminated substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510042401 CN1660939A (en) | 2005-01-24 | 2005-01-24 | Anticorrosive heat retaining rigid foam of asphaltum polyurethane modified by polyether glycol of organic aminated substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1660939A true CN1660939A (en) | 2005-08-31 |
Family
ID=35010504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510042401 Pending CN1660939A (en) | 2005-01-24 | 2005-01-24 | Anticorrosive heat retaining rigid foam of asphaltum polyurethane modified by polyether glycol of organic aminated substance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1660939A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100523084C (en) * | 2007-04-20 | 2009-08-05 | 常熟佳发化学有限责任公司 | Polyurethane resin combination and preparation method and using method thereof |
| CN101370983B (en) * | 2006-01-20 | 2012-02-29 | 拜尔材料科学股份公司 | Ballast roadbed and method for manufacturing ballast roadbed |
| CN103204747A (en) * | 2013-03-18 | 2013-07-17 | 江苏瑞丰科技实业有限公司 | Nutritional composite gel material for soil improvement |
| CN105622884A (en) * | 2016-04-06 | 2016-06-01 | 苏州甫众塑胶有限公司 | Organic foam thermal-insulation building material and preparation method thereof |
-
2005
- 2005-01-24 CN CN 200510042401 patent/CN1660939A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101370983B (en) * | 2006-01-20 | 2012-02-29 | 拜尔材料科学股份公司 | Ballast roadbed and method for manufacturing ballast roadbed |
| CN100523084C (en) * | 2007-04-20 | 2009-08-05 | 常熟佳发化学有限责任公司 | Polyurethane resin combination and preparation method and using method thereof |
| CN103204747A (en) * | 2013-03-18 | 2013-07-17 | 江苏瑞丰科技实业有限公司 | Nutritional composite gel material for soil improvement |
| CN105622884A (en) * | 2016-04-06 | 2016-06-01 | 苏州甫众塑胶有限公司 | Organic foam thermal-insulation building material and preparation method thereof |
| CN105622884B (en) * | 2016-04-06 | 2018-08-21 | 温州包鹿新材料有限公司 | A kind of organic foam heat-insulating construction material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1232557C (en) | polyurethane elastomer, preparation method and application thereof | |
| CN1146615C (en) | Siloxanes surface activater for producing apertured polyurethane flexible foam | |
| CN1146607C (en) | Polyurethane plastic foam | |
| CN1277895C (en) | Rigid polyurethane foams | |
| RU2679617C2 (en) | Process for preparation of solid polyurethane foam or urethane modified polyisocyanurate foam | |
| CN1404503A (en) | Rigid polyurethane foams | |
| CN1293114C (en) | Composite foam plastic with improved water-resistance, long storage time and short demoulding time | |
| CN1746203A (en) | Pur/pir rigid foams based on aliphatic polyester polyols | |
| CN1061416A (en) | By isocyanate-terminated prepolymer and with its preparation flexible polyurethane foam | |
| CN101044180A (en) | Method for the production of rigid polyurethane foams | |
| CN1142851C (en) | Composite elements containing compact polyisocyanate polyaddition products | |
| CN1221588C (en) | Method and device for producing polyester polyol, polyester polyol and polurethane foam | |
| CN1178803A (en) | Production of rigid polyurethane plastic foams | |
| CN101307129B (en) | Polyurethane/organic montmorillonite nano composite material and method for preparing same | |
| CN1251115A (en) | Method for preparing rigid polyurethane foam | |
| CN1519264A (en) | Low acid organic metallic catalyst for producing soft, semisoft and hard urethane foam | |
| CN102070412B (en) | Flame-retardant polyether glycol and preparation method thereof, combined polyether and polyurethane foam | |
| RU2009124292A (en) | REDUCING VOC EMISSIONS FROM NVH LOW DENSITY POLYURETHANE FOAMS TO FILL VACANCIES | |
| CN1660939A (en) | Anticorrosive heat retaining rigid foam of asphaltum polyurethane modified by polyether glycol of organic aminated substance | |
| CN1662588A (en) | Polyurethane or polyisocyanurate foams blown with hydrofluorocarbons and carbon atoms | |
| CN1074007C (en) | Method for making insulating rigid polyurethane foams | |
| CN1111553C (en) | The manufacture method of the urethane-rigid foam of hydrocarbon compound foaming | |
| CN1129621C (en) | Rigid polyurethane foams and method to form said foams using low molecular weight diols and triols | |
| CN1142513A (en) | Process for preparing open-cellular rigid polyurethane foam | |
| CN1072977C (en) | Apparatus for mixing of low-boiling foaming agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |