CN104387595A - Preparation method of compound slow-breaking slow-curing positive ion asphalt emulsifier - Google Patents
Preparation method of compound slow-breaking slow-curing positive ion asphalt emulsifier Download PDFInfo
- Publication number
- CN104387595A CN104387595A CN201410777205.0A CN201410777205A CN104387595A CN 104387595 A CN104387595 A CN 104387595A CN 201410777205 A CN201410777205 A CN 201410777205A CN 104387595 A CN104387595 A CN 104387595A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- add
- formaldehyde
- emulsifier
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to the field of organic fine chemicals, in particular to a preparation method of a compound slow-breaking slow-curing positive ion asphalt emulsifier. The preparation method is characterized by comprising the following steps: dissolving lignin in a sodium hydroxide solution, and adding aliphatic amine; heating the sodium hydroxide solution and then adding formaldehyde for reaction; adding glycidyl trimethyl ammonium chloride for reaction; adding a polyoxyethylene ether nonionic surfactant for reaction; adding formaldehyde and polyethylene polyamine to continue reaction, and then adding a diluent for dilution to obtain the emulsifier. When the emulsifier prepared by the method is used for preparing an asphalt emulsion, the usage amount of the emulsifier is small, and the emulsifier is applicable to various stone and can be widely applied to the prime coat oil, the slurry seal and the like of an asphalt road.
Description
Technical field
The present invention relates to organic fine chemicals field, be specifically related to a kind of compound preparation method splitting slow hardening cation asphalt emulgent slowly.
Background technology
Along with the development of road traffic, pitch is widely used in road construction construction.But pitch is a kind of semi-solid sticky shape material at normal temperatures, viscosity is large, mobility is very poor, only have and it is converted into liquid state just can be used by the method for heating, this causes inconvenience to construction, and bitumen emulsion is a kind of by under the effect of mechanical stirring or shearing, under asphalt emulsifier exists, the pitch of a kind of hot melt formed is with the tiny bitumen emulsion of particulate stable dispersion in water, and this bitumen emulsion is in a liquid state at normal temperatures, is easy to use.
Bitumen emulsion is the heterogeneous system of a high dispersing in essence, is system unstable on thermodynamics.Containing oleophylic and hydrophilic two kinds of groups in asphalt emulsifier structure, in bitumen emulsion, the lipophilic group of emulsifier molecules inserts in bitumen particle, and hydrophilic radical then inserts in water.Emulsifier molecules is formed on the surface of bitumen particle and aligns, and makes bitumen particle surface form the interfacial film that one deck has certain physical strength, is surrounded on this bitumen particle surface.This constructional feature can strengthen the avidity of bitumen particle to medium, reduces the interfacial tension of bitumen particle, makes pitch particle be not easy coagulation.The hydrophilic radical of ionic asphalt emulsification agent molecule also can ionize in water, makes electric charge on hydrophilic radical band, thus makes bitumen particle surface charging, and the electrostatic repulsion forces produced therefrom also can make, between bitumen particle, coagulation is less likely to occur.In addition, SURFACTANT ADSORPTION in system or be looped around pitch particle surface time, its space structure is larger, and the space length between besieged bitumen particle is also larger, be not easy contact, this space repulsion produced due to overlap can increase the stability of bitumen emulsion further.
Asphalt emulsifier is mainly divided into anionic asphalt emulsion, cation asphalt emulgent, zwitter-ion asphalt emulsifier and non-ionic type asphalt emulsifier.Relative to the asphalt emulsifier of other type, cation asphalt emulgent has obvious advantage in application and performance, generally speaking building stones are electronegative, ammonium ion in cation asphalt emulgent molecule hydrophilic group can with stone surface by electrostatic interaction generation strong adsorption, combine securely, thus enhance the adhesivity between pitch and building stones.So in recent years various countries all to develop cationic emulsifier, comprising quaternary ammonium salt, xylogen amine, alkyl polyamine class, amides and imidazolines etc.
Single emulsifying agent is not in use well positioned to meet the needs that bitumen emulsion is produced and used, the stability of such as bitumen emulsion is undesirable, cost is higher, breakdown of emulsion and shaping situation can not meet the demands etc., therefore by different emulsifying agents with the use of, thus strengthen the emulsifying capacity of emulsifying agent, reduce the production cost of bitumen emulsion, the pavement performance improving bitumen emulsion is the research emphasis of the industry.
Summary of the invention
The invention discloses a kind of compound preparation method splitting slow-curing asphalt emulsifying agent slowly, when preparing bitumen emulsion by the method, emulsifying agent usage quantity is few, and the building stones be suitable for are wide, can be widely used in the priming oil of bituminous pavement and slurry seal etc.
Preparation method of the present invention in turn includes the following steps:
A, be dissolved in sodium hydroxide solution by xylogen, add aliphatic amide, wherein the weight ratio of xylogen and aliphatic amide is 2:1 ~ 4:1:
Add formaldehyde reaction after b, intensification, the mol ratio of formaldehyde and aliphatic amide is 0.5:1 ~ 2:1;
C, add epoxypropyltrimethylchloride chloride reaction, the weight of epoxypropyltrimethylchloride chloride is 0.8 ~ 1.2 times of xylogen and aliphatic amide gross weight;
D, add polyethenoxy ether class nonionic surface active agent reaction, polyethenoxy ether class nonionic surface active agent weight is 2 ~ 5 times of xylogen and aliphatic amide gross weight;
E, add after formaldehyde and polyethylene polyamine continue reaction, add thinner and dilute and get final product, wherein the weight of polyethylene polyamine is 10 ~ 30% of xylogen weight, and the mol ratio of formaldehyde and polyethylene polyamine is 1.5:1 ~ 3:1.
In above-mentioned a step, the pH value of solution preferably controls between 9 ~ 11.
60 ~ 80 DEG C are preferably warming up to, preferably 0.5 ~ 3 hour reaction times in b step.
Preferably 2 ~ 8 hours step c reaction times.
Temperature of reaction preferably 60 ~ 80 DEG C in Step d, preferably 0.5 ~ 3 hour reaction times.
In step e, preferred reaction adds thinner after 0.5 ~ 3 hour again.
One or more preferably in amino dodecane, tetradecy lamine, cetylamine, stearylamine of above-mentioned aliphatic amide; Formaldehyde is paraformaldehyde or formaldehyde solution.
One or more preferably in polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, aliphatic amine polyoxyethylene ether and paregal O of polyethenoxy ether class nonionic surface active agent.Wherein polyoxyethylene octylphenol ether is as OP-10, OP-13 or OP-15 etc.Polyoxyethylene nonylphenol ether is as TX-10, TX-12, TX-15, TX-18 or TX-20 etc.Aliphatic amine polyoxyethylene ether is as AC-1810, AC-1812, AC-1815 etc.Paregal O is as O-15 or O-20 etc.
One or more preferably in diethylenetriamine, triethylene tetramine, tetraethylene pentamine of polyethylene polyamine.
One or more preferably in water, methyl alcohol, Virahol of thinner.
With cetylamine, OP-10 and diethylenetriamine are example, and reaction process of the present invention is as following reaction formula:
The present invention take xylogen as raw material, by Mannich and quaterisation, enhance the emulsifying property of xylogen, add polyethenoxy ether class nonionogenic tenside and ETA reacts, change the charging property of part Soxylat A 25-7 non-ionic type, improve the emulsifying capacity of asphalt emulsifier and the stability of bitumen emulsion, add formaldehyde and polyethylene polyamine in the final stage of reaction, strengthen the water-soluble and emulsified bitumen of xylogen and the bounding force of building stones further.Few according to asphalt emulsifier consumption prepared by this method, the bitumen emulsion good stability prepared with this emulsifying agent, indices is all better than national standard, and concrete data are shown in embodiment 1-5 medium pitch emulsion property test value.
Under same experimental conditions, compare the function of emulsifying agent of the present invention and commercial emulsifier, it is few that emulsifier of the present invention compares home products consumption, and emulsifying capacity is strong, the pitch of the multiple trade mark of energy emulsification.With bitumen emulsion prepared by commercial emulsifier, the stability of 5 days just reaches the standard of 5% of national defined, and uses emulsifying agent of the present invention, and the bitumen emulsion stability of 5 days is all less than 4%, be better than national standard, and its use properties does not change with the storage time.In addition the building stones adaptability of our product is extensive, and the more domestic existing emulsifying agents of the bitumen emulsion energy mix prepared by it can not the building stones of mix, and can realize the adjustment of duration of mixing, compensate for the domestic blank splitting slow-curing asphalt emulsifying agent slowly.
The invention has the advantages that: the source mainly paper making pulp industry of xylogen, is raw material with xylogen, belongs to renewable resources, and low price.Whole synthesis technique is simple, and processing condition easily realize, and do not have three waste discharge in preparation process, meets the environmental protection policy of country.Utilize aliphatic amide, epoxypropyltrimethylchloride chloride (ETA) and polyethylene polyamine carry out modification to xylogen, can strengthen the water-soluble and emulsifying capacity of xylogen, the lignin quaternary of synthesis has good solubility in all pH value environment.The reaction product that aliphatic amide and ETA react also has good emulsifying property.Nonionogenic tenside is added and xylogen carries out composite in reaction process, asphalt emulsifier can be made to have stronger emulsifying capacity and to the better adaptability of petroleum pitch, the composite use of this positively charged ion and nonionic emulsifier, the consumption of asphalt emulsifier can be made greatly to reduce, and the stability of bitumen emulsion is further enhanced.
Embodiment
Embodiment 1
The preparation of emulsifying agent
8g xylogen is dissolved in 35g water, be 9 by the pH value of sodium hydrate regulator solution, 2g amino dodecane is added in system, after system is warming up to 65 DEG C, add paraformaldehyde 0.4g, react after 1 hour, add epoxypropyltrimethylchloride chloride (ETA) 12g, react after 7 hours, add 40g OP-13, continue reaction after 1.5 hours, add 1g triethylene tetramine and 0.5g paraformaldehyde, continue reaction 1.5 hours, add massfraction 50% methanol solution and dilute and obtain and of the present inventionly split slow hardening type cation asphalt emulgent slowly.
The preparation of bitumen emulsion
Take the emulsifying agent (effective content is 50%) of the above-mentioned preparation of 10g, add the water of about 170ml, stir gently, to be emulsified dose completely dissolve after, be 2.0 with the pH of hydrochloric acid conditioning solution, and be settled to 200ml, obtain emulsifier aqueous solution.Unlatching emulsifying collid grind, the emulsifier aqueous solution being preheated to 50-60 DEG C is poured in colloidal mill, then the 300g petroleum pitch being heated to 130 ~ 140 DEG C is poured in colloidal mill while stirring, after circular grinding lmin, bitumen emulsion.
Bitumen emulsion performance test
Embodiment 2
The preparation of emulsifying agent
8g xylogen is dissolved in 35g water, be 9 by the pH value of sodium hydrate regulator solution, 4g stearylamine is added in system, after system is warming up to 75 DEG C, add paraformaldehyde 0.3g, react after 1 hour, add epoxypropyltrimethylchloride chloride (ETA) 14g, react after 3 hours, add 25g TX-15, continue reaction after 1 hour, add 2g tetraethylene pentamine and 0.6g paraformaldehyde, continue reaction 1 hour, add massfraction 50% methanol solution and dilute and obtain and of the present inventionly split slow hardening type cation asphalt emulgent slowly.
The preparation of bitumen emulsion is with embodiment 1.
Bitumen emulsion performance test
Embodiment 3
The preparation of emulsifying agent
8g xylogen is dissolved in 35g water, be 10 by the pH value of sodium hydrate regulator solution, 2g cetylamine is added in system, after system is warming up to 65 DEG C, add paraformaldehyde 0.3g, react after 1.5 hours, add epoxypropyltrimethylchloride chloride (ETA) 10g, react after 4 hours, add 20g TX-15 and 20g AC-1815, continue reaction after 1.5 hours, add 1g diethylenetriamine and 0.5g paraformaldehyde, continue reaction 1.5 hours, add 50% methanol solution and dilute and obtain and of the present inventionly split slow hardening type cation asphalt emulgent slowly.
The preparation of bitumen emulsion is with embodiment 1.
Bitumen emulsion performance test
Embodiment 4
The preparation of emulsifying agent
8g xylogen is dissolved in 35g water, be 11 by the pH value of sodium hydrate regulator solution, 2g cetylamine and 2g stearylamine is added in system, after system is warming up to 65 DEG C, add paraformaldehyde 0.3g, react after 2 hours, add epoxypropyltrimethylchloride chloride (ETA) 14g, react after 3 hours, add 32g TX-15, continue reaction after 1.5 hours, add 1g triethylene tetramine and 1g tetraethylene pentamine and 0.7g paraformaldehyde, continue reaction 1.5 hours, add massfraction 50% methanol solution and dilute and obtain and split slow hardening type cation asphalt emulgent slowly.
The preparation of bitumen emulsion is with embodiment 1.
Bitumen emulsion performance test
Embodiment 5
The preparation of emulsifying agent
8g xylogen is dissolved in 35g water, be 11 by the pH value of sodium hydrate regulator solution, 2g tetradecy lamine is added in system, after system is warming up to 85 DEG C, add paraformaldehyde 0.2g, react after 0.5 hour, add epoxypropyltrimethylchloride chloride (ETA) 11g, react after 2 hours, add 30g TX-15 and 10g O-15, continue reaction after 0.5 hour, add 1g diethylenetriamine and 1g triethylene tetramine and 1g paraformaldehyde, continue reaction 0.5 hour, add massfraction 50% methanol solution and dilute and obtain and split slow hardening type cation asphalt emulgent slowly.
The preparation of bitumen emulsion is with embodiment 1.
Bitumen emulsion performance test
Claims (10)
1. the compound preparation method splitting slow hardening cation asphalt emulgent slowly, in turn includes the following steps:
A, be dissolved in sodium hydroxide solution by xylogen, add aliphatic amide reaction, wherein the weight ratio of xylogen and aliphatic amide is 2:1 ~ 4:1:
Add formaldehyde reaction after b, intensification, the mol ratio of formaldehyde and aliphatic amide is 0.5:1 ~ 2:1;
C, add epoxypropyltrimethylchloride chloride reaction, the weight of epoxypropyltrimethylchloride chloride is 0.8 ~ 1.2 times of xylogen and aliphatic amide gross weight;
D, add polyethenoxy ether class nonionic surface active agent reaction, polyethenoxy ether class nonionic surface active agent weight is 2 ~ 5 times of xylogen and aliphatic amide gross weight;
E, add formaldehyde and polyethylene polyamine and continue reaction, add thinner and dilute and get final product, wherein the weight of polyethylene polyamine is 10 ~ 30% of xylogen weight, and the mol ratio of formaldehyde and polyethylene polyamine is 1.5:1 ~ 3:1.
2. the preparation method of claim 1, wherein in a step, the pH value of solution controls between 9 ~ 11.
3. the preparation method of claim 1, is wherein warming up to 60 ~ 80 DEG C in b step, the reaction times is 0.5 ~ 3 hour.
4. the preparation method of claim 1, wherein the step c reaction times is 2 ~ 8 hours.
5. the preparation method of claim 1, wherein in Step d, temperature of reaction is 60 ~ 80 DEG C, and the reaction times is 0.5 ~ 3 hour.
6. the preparation method of claim 1, wherein reacts in step e after 0.5 ~ 3 hour and adds thinner again.
7. the preparation method of claim 1, wherein aliphatic amide is selected from one or more in amino dodecane, tetradecy lamine, cetylamine, stearylamine; Formaldehyde is paraformaldehyde or formaldehyde solution.
8. the preparation method of claim 1, wherein polyethenoxy ether class nonionic surface active agent is selected from one or more in polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, aliphatic amine polyoxyethylene ether, paregal O.
9. the preparation method of claim 1, wherein polyethylene polyamine is selected from one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine.
10. the preparation method of claim 1, wherein thinner is selected from one or more in water, methyl alcohol, Virahol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410777205.0A CN104387595B (en) | 2014-12-16 | 2014-12-16 | Preparation method of compound slow-breaking slow-curing positive ion asphalt emulsifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410777205.0A CN104387595B (en) | 2014-12-16 | 2014-12-16 | Preparation method of compound slow-breaking slow-curing positive ion asphalt emulsifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104387595A true CN104387595A (en) | 2015-03-04 |
| CN104387595B CN104387595B (en) | 2017-01-11 |
Family
ID=52605564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410777205.0A Active CN104387595B (en) | 2014-12-16 | 2014-12-16 | Preparation method of compound slow-breaking slow-curing positive ion asphalt emulsifier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104387595B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903397A (en) * | 2017-11-29 | 2018-04-13 | 沈阳化工研究院有限公司 | A kind of high-performance cold renewal type asphalt emulsifier and preparation method thereof |
| CN108467495A (en) * | 2018-05-15 | 2018-08-31 | 苏州太星新材料科技有限公司 | A kind of lignin quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
| CN108485293A (en) * | 2018-05-15 | 2018-09-04 | 苏州太星新材料科技有限公司 | A kind of fibrination ethers quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
| CN110437346A (en) * | 2019-07-03 | 2019-11-12 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | A kind of preparation method of functional form chemical industry emulsifier |
| CN115746331A (en) * | 2022-11-22 | 2023-03-07 | 济南圣泉集团股份有限公司 | Slow-breaking and medium-condensing asphalt emulsifier for cold regeneration, silicon dioxide modified lignin amine, emulsified asphalt and preparation method |
| CN116874095A (en) * | 2023-09-06 | 2023-10-13 | 杭州尚善若水环保科技有限公司 | Phosphorus-free mixture for boiler shutdown protection and daily operation dosing treatment |
-
2014
- 2014-12-16 CN CN201410777205.0A patent/CN104387595B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 刘祖广等: ""高级脂肪胺/甲醛改性木质素季铵盐的制备及基本表面物化性能"", 《化工学报》 * |
| 张彤: ""阳离子表面活性剂的合成、性能及在乳化沥青中的应用"", 《万方中国学位论文全文数据库 应用化学》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903397A (en) * | 2017-11-29 | 2018-04-13 | 沈阳化工研究院有限公司 | A kind of high-performance cold renewal type asphalt emulsifier and preparation method thereof |
| CN107903397B (en) * | 2017-11-29 | 2020-10-16 | 沈阳化工研究院有限公司 | High-performance cold-recycling asphalt emulsifier and preparation method thereof |
| CN108467495A (en) * | 2018-05-15 | 2018-08-31 | 苏州太星新材料科技有限公司 | A kind of lignin quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
| CN108485293A (en) * | 2018-05-15 | 2018-09-04 | 苏州太星新材料科技有限公司 | A kind of fibrination ethers quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
| CN110437346A (en) * | 2019-07-03 | 2019-11-12 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | A kind of preparation method of functional form chemical industry emulsifier |
| CN115746331A (en) * | 2022-11-22 | 2023-03-07 | 济南圣泉集团股份有限公司 | Slow-breaking and medium-condensing asphalt emulsifier for cold regeneration, silicon dioxide modified lignin amine, emulsified asphalt and preparation method |
| CN115746331B (en) * | 2022-11-22 | 2024-05-10 | 济南圣泉集团股份有限公司 | Slow-cracking middle-setting asphalt emulsifier for cold recycling, silica modified lignin amine, emulsified asphalt and preparation method thereof |
| CN116874095A (en) * | 2023-09-06 | 2023-10-13 | 杭州尚善若水环保科技有限公司 | Phosphorus-free mixture for boiler shutdown protection and daily operation dosing treatment |
| CN116874095B (en) * | 2023-09-06 | 2023-12-15 | 杭州尚善若水环保科技有限公司 | Phosphorus-free mixture for boiler shutdown protection and daily operation dosing treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104387595B (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104387595A (en) | Preparation method of compound slow-breaking slow-curing positive ion asphalt emulsifier | |
| CN102863804B (en) | SBS polymer modified emulsified asphalt and preparation method | |
| CN101643584B (en) | Modified emulsified asphalt with excellent temperature adaptability and preparation method thereof | |
| CN105399645A (en) | Multi-positive-ion amide-type asphalt emulsifier and preparation method thereof | |
| CN105418942A (en) | Dicationic amide type asphalt emulsifier and preparation method therefor | |
| CN103073731B (en) | Preparation method of cold-recycling lignin asphalt emulsifier | |
| CN104530445B (en) | A kind of preparation method splitting fast solidifying type asphalt emulsifier slowly | |
| CN102675890A (en) | Demulsifying slow breaking and quick setting modified emulsified asphalt by microwave heating and preparation method thereof | |
| CN106084250A (en) | A kind of lignin cyclammonium cationoid type asphalt emulsifier and preparation method thereof | |
| CN108342089B (en) | Modified emulsified asphalt and preparation method thereof | |
| CN102031001B (en) | Road bentonite-based emulsified asphalt and preparation method thereof | |
| CN103274972B (en) | Synthesis method of zwitterion type modified asphalt emulsifier and modified emulsified asphalt containing emulsifier | |
| CN104693043A (en) | An improvement in a synthesis process for a saturated aliphatic amine cation asphalt emulsifier | |
| CN106832328B (en) | Retarder applied to emulsified asphalt plant-mixed cold-recycling mixture and preparation method thereof | |
| CN104693454A (en) | P-10 nonionic/cationic composite asphalt emulsifier | |
| CN100457830C (en) | High-performance Sasobit and SBR modified emulsified asphalt, and its preparation method and uses | |
| CN110591399A (en) | Modified emulsified asphalt with high viscosity and high softening point and preparation method thereof | |
| CN104693053A (en) | Process for synthesizing novel betaine-type asphalt emulsifier from laurinol | |
| CN108467495A (en) | A kind of lignin quaternary ammonium salt cation asphalt emulsifier and preparation method thereof | |
| CN104693048A (en) | Nonylphenol polyoxyethylene ether slow cracking fast setting type asphalt emulsifier synthesis process | |
| CN112521623A (en) | Lignin emulsifier, asphalt emulsifier, preparation method of asphalt emulsifier and asphalt | |
| CN103709259B (en) | Acid modified starch positively charged ion splits the preparation method of slow-curing asphalt emulsifying agent slowly | |
| KR100982350B1 (en) | Emulsion additive for regenerated ascon and producing method for the same | |
| CN108359256B (en) | Emulsified modified asphalt based on zwitterionic Gemini emulsifier and preparation method thereof | |
| CN117126544B (en) | Compound emulsified asphalt, and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |