CN102633988A - Modified lauryl amine hardener, manufacturing method and application of modified lauryl amine hardener - Google Patents
Modified lauryl amine hardener, manufacturing method and application of modified lauryl amine hardener Download PDFInfo
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- CN102633988A CN102633988A CN201210129951XA CN201210129951A CN102633988A CN 102633988 A CN102633988 A CN 102633988A CN 201210129951X A CN201210129951X A CN 201210129951XA CN 201210129951 A CN201210129951 A CN 201210129951A CN 102633988 A CN102633988 A CN 102633988A
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- lauryl amine
- water
- mibk
- amine hardener
- solidifying agent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
The invention relates to a modified lauryl amine hardener and a manufacturing method and application of the modified lauryl amine hardener. The structural formula of the modified lauryl amine hardener is shown in the description. The manufacturing method of the modified lauryl amine hardener comprises the following steps: (1) adding lauryl amine and methyl isobutyl ketone (MIBK) in molar ratio of 1:1.2-2 in a four-opening flask with a stirring device, a thermometer and a water segregator; (2) stirring, leading counterflow of reaction to start to appear after heating temperature from common temperature to 71-75 DEG C, carrying over generated water by the MIBK with the performance of the reaction, achieving reaction end after gradually heating to 118-121 DEG C and reacting to that fact that water isn't generated any more; and (3) decreasing the temperature to 70-80 DEG C, obtaining excessive MIBK for recycle through reduced pressure distillation, and finally obtaining a modified lauryl amine hardener product. The modified lauryl amine hardener can be applied as a treating agent for solidification in the field of oil field sand prevention and can be manufactured to be a polyurethane waterproofing paint.
Description
Technical field
The present invention relates to a kind of modified amine curing agent.
Background technology
Epoxy resin is the important resin matrix of coating, tackiness agent, insulating material and matrix material.Common epoxyn is two component systems, its advantage be just begin reaction after mixing can be in room temperature or more low temperature curing down.Epoxy resin in two component systems can not be long time stored after mixing with solidifying agent; Must be respectively charged into storage and custody in the container; Must in its duration of service, use up after the mixing, not use up mixture and can not use again, and mix back viscosity and slowly rise; Can not under controlled condition, operate, be difficult to realize operation automation.During construction two component married operations often, error in dipping, regular meetings such as undercompounding cause that curing is not thorough.Thereby the development operating procedure is simple, and environmental pollution is little, and stability in storage is good, the time is long, and the monocomponent epoxide-resin rubber adhesive that quality product is high is particularly important.The design that focuses on the solidifying agent molecule and the selection of research and development at present, wherein the research and development of latent curing agent are the most active and important.This type solidifying agent mainly is through temporary transient sealing or some reactive behavior height of passivation and the reactive group and the structure of the solidifying agent of package stability difference are implemented.Have good room temperature, the package stability under the normal pressure after this type solidifying agent joins in the epoxy resin, can make metastable solidifying agent by different mechanisms activation and participate in the curing of epoxy resin during use by means of the chemical factors that moisture, light, heat or pressure etc. add.Up to now studying maximum latent curing agents is ketoimine.This type of solidifying agent can carry out the nucleophilic addition(Adn) dehydration by fatty amine and ketone and make.Because the characteristic of molecular structure, it mixes with epoxy resin, and the one-component epoxy adhesive that constitutes can water in air be divided or the moisture that contacts moist bonding plane dissociates solidifying agent through absorbing, and discharges aminated compounds again and makes epoxy resin cure.
The urethane full name is a polyurethane(s), contains repetition carbamate groups (NHCOO) on its main chain, forms through organic diisocyanate or POLYMETHYLENE POLYPHENYLISOCYANATE and dihydroxyl or polyol addition polymerization.Polyurethane water-proof paint is a kind of novel high-grade water-proof and anti-corrosive material; The base layer construction that is fit to any complicacy; Be particularly suitable for the roofing of special construction, waterproof, the antiseepage in vault and bathroom, lavatory, and the anticorrosion chinampa and the elastic ground etc. of also can be used as of chemical industry ground and pipeline.The monocomponent polyurethane waterproof paint is to be main raw material with isocyanic ester, polyethers, is equipped with the response type flexible waterproof coating that various auxiliary agents are processed.Single-component water cure polyurethane coating utilizes isocyanic ester and water cure generation serial reaction, reaches chain extension and the effect of solidifying isocyanic ester, and its easy construction is nuisanceless, helps environmental protection, is the developing direction of polyurethane water-proof paint.
Summary of the invention
Technical problem to be solved by this invention is to above-mentioned prior art a kind of modification amino dodecane solidifying agent to be provided; It is nontoxic, good stability, can be moist or have the cured article intensity of using in the low temperature environment in the water and forming with the epoxy resin reaction high; Single-component system by this solidifying agent and epoxy resin mixed preparing form can be placed the long period; Without field mix, simplify production, used technology, help to prevent the pollution of the environment.
Another object of the present invention provides that a kind of synthesis technique is simple, productive rate is high, can be used as the preparation method of the modification amino dodecane solidifying agent of urethane moisture-curable.
The present invention addresses the above problem the scheme of being taked to be: modification amino dodecane solidifying agent has following structural formula
The technical scheme that preparation method of the present invention adopted is: the preparation method of modification amino dodecane solidifying agent includes following steps:
1) in the four-hole boiling flask that has whipping appts, TM and water trap, adding is the amino dodecane and the MIBK of 1:1.2 ~ 2 in molar ratio, and in water trap, fills it up with MIBK just;
2) stir, be warming up to 71 ~ 95 ℃ of reactions from normal temperature and begin occur to reflux, along with the carrying out of reaction, the water of generation is taken out of by methyl isobutyl ketone (MIBK), is warming up to 118 ~ 121 ℃ more gradually, reacts no longer to produce water to system and be reaction end;
3) be cooled to 70 ~ 80 ℃ then, underpressure distillation goes out excessive MIBK to recycle, and promptly gets product modification amino dodecane solidifying agent.
Modification amino dodecane solidifying agent of the present invention is as the application of oil field sand prevention field solidification treatment agent; Described modification amino dodecane solidifying agent and bisphenol A type epoxy resin can be mixed with the single-component sand-fixing agent; But it is coated in the precoated sand long-term storage of the quartz sand surface gained that is mixed with coupling agent; Be filled in the middle low temperature oil well of water environment can the anti-folding of fixed formation and ultimate compression strength high, anti-washing away, the core rock stratum that good penetrability and resistance to medium are excellent.
Modification amino dodecane solidifying agent of the present invention is as the application of preparation polyurethane water-proof paint; Described modification amino dodecane solidifying agent can be at moist basal plane curing urethane sizing agent; Form the dense film that one deck has strong hydrophobic nature; This coated film has higher tensile strength, and is ageing-resistant and acid-alkali-corrosive-resisting property is good.This waterproof paint can be used for skin and indoor waterproof.
The primitive reaction equation of the present invention's reaction:
The modification amino dodecane solidifying agent of the present invention's preparation is compared with existing ketoimine solidifying agent, and its preparation technology is simple, and volatility of raw material property and toxicity are low; Feed stock conversion is high, and product stability is good, and the cured article cross-linking density is high; Be specially adapted to the epoxy resin outdoor work and be used for coating, civil construction and oilfield sand control field etc., (1,3-dimethyl--butylidene)-lauryl amine of gained is light yellow transparent liquid; Fusing point is-27.3 ℃, 290 ℃ of boiling points, density 819.4kg/m
3(25 ℃), viscosity 2022mPas (25 ℃), the amine value 303 (mgKOH/g) after its hydrolysis, the reactive hydrogen equivalent is 185, hectogram standard epoxy (epoxy equivalent (weight) EEW=190) consumption is 70.
Description of drawings
Fig. 1 is the infared spectrum of (1,3-dimethyl--butylidene)-lauryl amine;
Fig. 2 is the mass spectrum of (1,3-dimethyl--butylidene)-lauryl amine.
Specific embodiment:
Below in conjunction with embodiment the present invention is done further detailed description, but this explanation can not be construed as limiting the invention.
In the 500ml four-hole boiling flask that has whipping appts, TM and water trap (water trap is equipped with reflux condensate device); Add the amino dodecane of 1mol and the MIBK of 1.2mol; In water trap, fill it up with MIBK just; Mechanical stirring also is heated to 95 ℃, and reaction begins to produce water and occur to reflux, along with the carrying out of reaction heat temperature raising to 118 ℃ gradually.The height of lower floor's liquid level (water surface) no longer increases and is reaction end in water trap.Emit lower floor's liquid (water that reaction produces) and measure its volume, can get the transformation efficiency of amino dodecane.Be cooled to 70 ℃, decompression (0.1MPa) distills out excessive MIBK, promptly gets product.Product is light yellow transparent liquid, and fusing point is-27.3 ℃, 290 ℃ of boiling points, density 819.4kg/m
3(25 ℃), viscosity 2022mPas (25 ℃).Amine value 303 (mgKOH/g) after its hydrolysis, the reactive hydrogen equivalent is 185, hectogram standard epoxy (epoxy equivalent (weight) EEW=190) consumption is 70.Can find out 2923cm from Fig. 1
-1And 2852cm
-1The strong sharp absorption peak that two places occur is the charateristic avsorption band of methylene, 1660cm
-1The place is the charateristic avsorption band of two keys (-N=C-), 1466cm
-1The place is the charateristic avsorption band of methyl.As shown in Figure 2, the molecular ion peak of (1,3-dimethyl--butylidene)-lauryl amine appears at 268, and abundance is 100%.This conforms to the theoretical value of title product.
Can be used as the latent moisture-curable agent of monocomponent polyurethane sizing agent with the foregoing description 1 products therefrom.This solidifying agent and urethane are mixed (by quality, hardener dose be adhesive for polyurethane 10%) be coated in moist basal planes such as vault, toilet or roof exterior wall, hang through room temperature and formed thin film in substrate surface in 3 ~ 4 days.Water droplet can natural landing on this film, and this film is closely knit, and waterproof layer is complete, leakless, and free of pinholes, no bubble not only has water-proof function but also the trapping function is arranged.
Embodiment 2
In having the 25L four-hole reaction flask of whipping appts, TM and water trap (water trap is equipped with reflux condensate device); Add the amino dodecane of 50mol and the MIBK of 75mol; In water trap, fill it up with MIBK just; Mechanical stirring also is heated to 95 ℃, and reaction begins to produce water and occur to reflux, along with the carrying out of reaction heat temperature raising to 118 ℃ gradually.The height of lower floor's liquid level (water surface) no longer increases and is reaction end in water trap.Emit lower floor's liquid (water that reaction produces) and measure its volume, can get the transformation efficiency of amino dodecane.Be cooled to 80 ℃, decompression (0.1MPa) distills out excessive MIBK, promptly gets product.Product is light yellow transparent liquid, and fusing point is-27.3 ℃, 290 ℃ of boiling points, density 819.4kg/m
3(25 ℃), viscosity 2022mPas (25 ℃).Amine value 303 (mgKOH/g) after its hydrolysis, the reactive hydrogen equivalent is 185, hectogram standard epoxy (epoxy equivalent (weight) EEW=190) consumption is 70.
The epoxy binder in monocomponent in its storage period long (system viscosity rises extremely slow) that is mixed with the foregoing description 2 gained solidifying agent and epoxy resin (E-51 or E-44); Generally can reach about 7 days, being specially adapted to need be in the civil construction and the paint field of outdoor long working.
Embodiment 3
The amino dodecane of input 320kg and the MIBK of 346kg in being equipped with the 1 ton of reaction kettle that divides water and reflux condensate device, agitator, steam heating is started the water of condensation water pump and is decompressed to-0.01MPa.Reaction begins to reflux and produce water when reactor temperature rises to 71 ℃, slowly is warming up to 101 ℃, and the water that reaction produces obviously reduces., the height of lower floor's liquid level (water surface) in the water trap is reaction end when no longer increasing.Emit lower floor's liquid continued and be warming up to 121 ℃, decompression (0.1MPa) distills out excessive MIBK (recycling).Stopped reaction is emitted reactant from the reaction kettle lower end.Product is light yellow transparent liquid, and fusing point is-27.3 ℃, 290 ℃ of boiling points, density 819.4kg/m
3(25 ℃), viscosity 2022mPas (25 ℃).Amine value 303 (mgKOH/g) after its hydrolysis, the reactive hydrogen equivalent is 185, hectogram standard epoxy (epoxy equivalent (weight) EEW=190) consumption is 70.
Be mixed with its shelf-time of precoated sand long (reaching 3 months) that single-component adhesive is prepared into the foregoing description 3 gained solidifying agent and epoxy resin (E-51 and E-20); The preparation method of precoated sand is: 45 weight part epoxy resin (E-51:E-20=1:3) and 20 parts by weight of ethanol are mixed wiring solution-forming; The above-mentioned solidifying agent of 2 weight parts that will prepare then joins in the above-mentioned solution, mixes; 2 weight part KH-550 are joined in the 1000 weight part silica sands in whisking appliance, stir, the solution that will go up step preparation then joins in the whisking appliance and mixes with sand; Above-mentioned preparatory parcel sand is scattered in air seasoning place, hang, behind the sand finish-drying to be wrapped it is ground diffusing, the pack sealing is preserved.
The preparation of fixed rock core: with precoated sand be filled into an end be equipped with plug with holes Glass tubing in promptly get fixed rock core after 2 days at 60 ℃ of following underwater curings.The fixed sand core strength that in the high wet environment of middle low temperature of oil well, forms is high, and (anti-folding and ultimate compression strength are respectively 6.4 ~ 8.5MPa and 10.2 ~ 13.6MPa), good penetrability (6.7 ~ 8.9 μ m
2), medium-resistance (60 after different media is soaked 15 days its intensity such as following table 1) is excellent.
The experiment of table 1 media-resistant
| The saturated NaCI diesel oil of medium clear water |
| Ultimate compression strength (MPa) 10.6 10.2 11.3 12.4 10.4 12.9 12.8 13.6 before soaking |
| Soak back ultimate compression strength (MPa) 10.9 11.3 10.4 10.3 8.9 6.3 13.2 14.9 |
Claims (4)
1. modification amino dodecane solidifying agent has following structural formula
2. the preparation method of the described modification amino dodecane of claim 1 solidifying agent includes following steps:
1) in the four-hole boiling flask that has whipping appts, TM and water trap, adding is the amino dodecane and the MIBK of 1:1.2 ~ 2 in molar ratio, and in water trap, fills it up with MIBK just;
2) stir, be warming up to 71 ~ 95 ℃ of reactions from normal temperature and begin occur to reflux, along with the carrying out of reaction, the water of generation is taken out of by methyl isobutyl ketone (MIBK), is warming up to 118 ~ 121 ℃ more gradually, reacts no longer to produce water to system and be reaction end;
3) be cooled to 70 ~ 80 ℃ then, underpressure distillation goes out excessive MIBK to recycle, and promptly gets product modification amino dodecane solidifying agent.
3. the described modification amino dodecane of claim 1 solidifying agent is as the application of oil field sand prevention field solidification treatment agent.
4. the described modification amino dodecane of claim 1 solidifying agent is as the application of preparation polyurethane water-proof paint.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210129951.XA CN102633988B (en) | 2012-04-28 | 2012-04-28 | Modified lauryl amine hardener, manufacturing method and application of modified lauryl amine hardener |
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| CN201210129951.XA CN102633988B (en) | 2012-04-28 | 2012-04-28 | Modified lauryl amine hardener, manufacturing method and application of modified lauryl amine hardener |
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| CN102633988A true CN102633988A (en) | 2012-08-15 |
| CN102633988B CN102633988B (en) | 2014-03-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194476A (en) * | 2014-09-19 | 2014-12-10 | 苏州中亚油墨有限公司 | Assistant for water-based ink |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6573357B1 (en) * | 1999-06-30 | 2003-06-03 | Resolution Performance Products Llc | Process for the preparation of ketimine curing agents |
| CN1576316A (en) * | 2003-07-09 | 2005-02-09 | 气体产品与化学公司 | Epoxy resin compositions |
| JP2008274172A (en) * | 2007-05-02 | 2008-11-13 | Yokohama Rubber Co Ltd:The | One-pack moisture-curable resin composition |
| CN101629047A (en) * | 2009-08-07 | 2010-01-20 | 上海瑞鹏化工材料科技有限公司 | Spraying polyurethane waterproof material and application technology thereof |
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2012
- 2012-04-28 CN CN201210129951.XA patent/CN102633988B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6573357B1 (en) * | 1999-06-30 | 2003-06-03 | Resolution Performance Products Llc | Process for the preparation of ketimine curing agents |
| CN1576316A (en) * | 2003-07-09 | 2005-02-09 | 气体产品与化学公司 | Epoxy resin compositions |
| JP2008274172A (en) * | 2007-05-02 | 2008-11-13 | Yokohama Rubber Co Ltd:The | One-pack moisture-curable resin composition |
| CN101629047A (en) * | 2009-08-07 | 2010-01-20 | 上海瑞鹏化工材料科技有限公司 | Spraying polyurethane waterproof material and application technology thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194476A (en) * | 2014-09-19 | 2014-12-10 | 苏州中亚油墨有限公司 | Assistant for water-based ink |
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