CN101735421B - Method for preparing phenolic resin pre-condensation polymer cross-linking agent - Google Patents
Method for preparing phenolic resin pre-condensation polymer cross-linking agent Download PDFInfo
- Publication number
- CN101735421B CN101735421B CN 200910231586 CN200910231586A CN101735421B CN 101735421 B CN101735421 B CN 101735421B CN 200910231586 CN200910231586 CN 200910231586 CN 200910231586 A CN200910231586 A CN 200910231586A CN 101735421 B CN101735421 B CN 101735421B
- Authority
- CN
- China
- Prior art keywords
- linking agent
- phenolic resin
- condensation polymer
- temperature
- resin pre
- 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.)
- Active
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention provides a method for preparing phenolic resin pre-condensation polymer cross-linking agent, which takes phenol, hydroquinone, methanol, urotropine, 40% of sodium hydroxide solution and water as raw materials and comprises the following steps: introducing cooling water into a reaction kettle; adding 10-15% of phenol, 15-10% of hydroquinone and 5-10% of sodium hydroxide solution with mass concentration of 40%; starting a stirrer, opening a cooling water valve, adjusting the cooling temperature to be not higher than 50 DEG C; adding 5-10% of urotropine when the cooling temperature is controlled below 40 DEG C, dissolving, adding 65-55% of methanol slowly when the temperature is controlled to be not higher than 50 DEG C; stirring and reacting for 20-30min after all the raw materials are added, discharging when the fact that the temperature rises without any fallout trend is observed to obtain the phenolic resin pre-condensation polymer cross-linking agent which has the advantages of simple use, low toxicity, environment protection, adjustable gelation time and temperature of jelly thereby, and good temperature tolerance.
Description
Technical field:
The present invention relates to a kind of oilfield chemistry with the preparation method of agent especially for the agent of preparation polymer gel retarded crosslinking.
Background technology:
Polymer gel is the viscoelastic body that polymkeric substance and the linking agent crosslinking reaction in the solution generates.Polymer gel is widely used in oil field profile control and water plugging and the TOR.Polymkeric substance commonly used is a partially hydrolyzed polyacrylamide (relative molecular mass 5 * 10
6～12 * 10
6, degree of hydrolysis 10%～25%), linking agent commonly used is that high volence metal ion is (like Cr
3+, Zr
4+, Al
3+, Ti
4+Deng), aldehyde (like formaldehyde, acetaldehyde, oxalic dialdehyde etc.) and resin (like resol) etc.Can form different frozen glue by different linking agents, like chromium gel, Zirconium gel, aluminium gel, titanium frozen glue, aldehyde frozen glue and resin frozen glue etc.Wherein (10min～24h), temperature tolerance is poor, and temperature surpasses 75 ℃ of instabilities, synersis for the crosslinked frozen glue gelation time weak point of high volence metal ion; The crosslinked condition of aldehyde frozen glue is harsh, and the pH value of being everlasting is less than just effective under 3 conditions, limited use; The resin frozen glue gelation time is long, and (1d～30d), temperature tolerance is good, (60～100 ℃) applied widely.Resin (like resol) is very common, is formed by phenols and aldehyde condensation polymer, is divided into thermoset and thermoplasticity, how to exist with solid-like, and is water insoluble because of it, is soluble in pure and mild ketone, the unsuitable water-soluble cross-linker of making polymer gel.Therefore the many monomers with phenols and aldehydes of resin cross-linking agent use, and need with sodium hydrogencarbonate or careless acid for adjusting pH value during use, but because toxicity, pungency and the insoluble of free phenols and aldehyde injure greatly operator, are unfavorable for environmental protection, restrict its use.
Summary of the invention:
The objective of the invention is to provide a kind of preparation method of phenolic resin pre-condensation polymer cross-linking agent, make prepared product have to use characteristics such as the frozen glue gelation time and intensity of simple, low toxic and environment-friendly, formation is adjustable, temperature tolerance is good.
The objective of the invention is to realize like this:
Used feed composition and the weight percent that respectively accounts for the raw material total amount are: phenol 10%～15%, Resorcinol 10%～15%, formaldehyde 55%～65%, urotropine 5%～10%, mass concentration are that 40% sodium hydroxide solution 5%～10% and surplus are water; Each component sum is one of percentage hundred, specifically preparation according to the following steps:
1. the logical water coolant of reaction kettle adds phenol, Resorcinol and sodium hydroxide solution according to the above ratio in reaction kettle, and best ratio is: phenol 11%～13%, Resorcinol 11%～13% and mass concentration are 40% sodium hydroxide solution 5%～8%;
2. start stirrer, open cooling water valve, adjustment cooling degree, the temperature in the control reaction kettle is not higher than 50 ℃;
3. the temperature in the question response still no longer raises; When being controlled at below 40 ℃, the ratio in 5%～10% adds urotropine, and optimum proportion is 7%～9%; After the dissolving; Slowly add formaldehyde in 55%～65% ratio again, optimum proportion is 60%～64%, and the control reactor temperature is no more than 50 ℃ during adding;
4. material all adds back stirring reaction 20min～30min, observes that temperature no longer raises and discharging when falling trend is arranged, and the temperature variation that still need continue to observe product after the discharging if temperature rising phenomenon is arranged, should in time be handled with water quench.
The invention has the beneficial effects as follows: by the phenolic resin pre-condensation polymer cross-linking agent low toxic and environment-friendly of method provided by the present invention preparation, the toxicity of monomer-free phenol and aldehyde and pungency, to compare toxicity lower with the high-valency metal chromium of using always.The retarded crosslinking performance is good, and crosslinking time is adjustable, gel strength is adjustable.Through the adjustment polymkeric substance (1000mg/L～5000mg/L) and linking agent (and the proportioning of 2000mg/L～15000mg/L), crosslinking time can be controlled in 1～30 day, the frozen glue viscosity of formation is 500mPa.s～100000mPa.s.Good with the formed frozen glue temperature tolerance of polymkeric substance, stable for a long time under 100 ℃ of conditions, not broken glue, and chromium gel surpasses the broken glue of very easy dehydration under 75 ℃ of conditions in temperature usually.Salinity to preparation water is applied widely, and when the mass concentration of HPAM is 3000mg/L, the linking agent mass concentration is 3000mg/L;, salinity all can form frozen glue in being lower than the 100000mg/L scope; Just salinity is high more, and the gelation time can be short more, but its Strength Changes is little.
Embodiment:
Specifically describe preparation process of the present invention below in conjunction with embodiment.
Prepare starting material: phenol, Resorcinol, formaldehyde, urotropine, mass concentration are 40% sodium hydroxide solution and water.
Embodiment 1:
Reaction kettle leads to water coolant, and adding phenol 120kg, Resorcinol 120kg and mass concentration are 40% sodium hydroxide solution 60kg in reaction kettle; Open stirrer, the adjustment cooling water valve, adjustment cooling degree, reactor temperature is not higher than 50 ℃; Treat that temperature no longer raises, when being controlled at below 40 ℃, after the adding urotropine 80kg dissolving, slowly add formaldehyde 620kg, the control reactor temperature is no more than 50 ℃ when noting adding; Material all adds back stirring reaction 20～30min, observes that temperature no longer raises and discharging when falling trend is arranged, and the discharging continued is observed the temperature variation of product, if temperature rising phenomenon is arranged, should in time handle with water quench.
In the key of entire synthesis process is that the control reactor temperature can not surpass 50 ℃, otherwise will cause implode, and the polymerization degree sharply increases, be difficult to produce degree of polycondensation appropriateness, can fine crosslinked product.
The method of use of the phenolic resin prepolymer condensation polymer linking agent of preparation: under agitation condition; Ratio in 0.3%～1.5% in the polymkeric substance for preparing (like partially hydrolyzed polyacrylamide) solution slowly adds phenolic resin prepolymer condensation polymer linking agent, gets final product after stirring.
Polymer gel is with the working conditions of phenolic resin pre-condensation polymer cross-linking agent: molecular weight 8,000,000～1,500 ten thousand that require partially hydrolyzed polyacrylamide; Degree of hydrolysis 15～30%; The preparation water salinity is no more than 80000mg/L; Frozen glue after crosslinked has the gelation time and gelation intensity is adjustable, and is stable for a long time under 100 ℃ of conditions.
The product that makes by above-mentioned steps is in first, second two oil field rig-site utilization: 65 ℃ of nail polish field reservoir temperatures; Preparation water salinity 32000mg/L, and the adjustment polymkeric substance (3000mg/L～5000mg/L) and linking agent (concentration of 6000mg/L～15000mg/L), the gelation time reaches 3～25 days; The frozen glue viscosity that forms is 1800mPa.s～80000mPa.s; Under 65 ℃ of conditions of reservoir temperature 3 months, the frozen glue viscosity retention ratio reached 99.9%, has good stability.95 ℃ of second oil field reservoir temperatures, preparation water salinity 19000mg/L, adjustment polymkeric substance (1000mg/L～4000mg/L) and the linking agent (concentration of 3000mg/L～10000mg/L); The gelation time reaches 1～20 day; The frozen glue viscosity that forms is 2600mPa.s～100000mPa.s, and under 95 ℃ of conditions of reservoir temperature 3 months, the frozen glue viscosity retention ratio also can be up to 98%; This is that other types frozen glue is difficult to realize, has good stability.
Embodiment 2:
Reaction kettle leads to water coolant, and phenol 100kg, Resorcinol 100kg and the mass concentration that adding has been melted in reaction kettle is 40% sodium hydroxide solution 50kg; Open stirrer, the adjustment cooling water valve, adjustment cooling degree, the control reactor temperature is not higher than 50 ℃; Treat that temperature no longer raises, when being controlled at below 40 ℃, after the adding urotropine 50kg dissolving, slowly add formaldehyde 550kg and excess water 150kg, the control reactor temperature is no more than 50 ℃ when noting adding; Material all adds back stirring reaction 20～30min, observes that temperature no longer raises and discharging when falling trend is arranged, and the discharging continued is observed the temperature variation of product, if temperature rising phenomenon is arranged, should in time handle with water quench.
By the product that above-mentioned steps makes, because the raw material additional proportion is low, it is low to make the product effective content; Therefore press the reservoir condition in nail polish field among the embodiment 1, the minimum working concentration of linking agent is greater than 8000mg/L, and the gelation time reaches 3～30 days; The frozen glue viscosity that forms is 1500mPa.s～72000mPa.s; Under 65 ℃ of conditions of reservoir temperature 3 months, the frozen glue viscosity retention ratio reached 99.5%, has good stability.
Embodiment 3:
Reaction kettle leads to water coolant, and phenol 150kg, Resorcinol 150kg and the mass concentration that adding has been melted in reaction kettle is 40% sodium hydroxide solution 50kg; Open stirrer, the adjustment cooling water valve, adjustment cooling degree, reactor temperature must not be higher than 50 ℃; Treat that temperature no longer raises, below 40 ℃ the time, add urotropine 100kg dissolving after, slowly add formaldehyde 550kg, the control reactor temperature is no more than 50 ℃ when noting adding; Material all adds back stirring reaction 20～30min, observes that temperature no longer raises and discharging when falling trend is arranged, and the discharging continued is observed the temperature variation of product, if temperature rising phenomenon is arranged, should in time handle with water quench.
By the product that above-mentioned steps makes, because phenol and urotropine additional proportion are high, it is higher to make the product effective content; Therefore press the reservoir condition in nail polish field among the embodiment 1, the working concentration of linking agent can be reduced to 4000mg/L, and the gelation time reaches 2～25 days; The frozen glue viscosity that forms is 2000mPa.s～75000mPa.s; Under 65 ℃ of conditions of reservoir temperature 3 months, the frozen glue viscosity retention ratio reached 99.0%, had stability preferably.But product became about 60 days by 90 days under the top condition steady time under 25 ℃ of normal temperature.
Claims (6)
1. the preparation method of a phenolic resin pre-condensation polymer cross-linking agent; It is characterized in that; Used raw material consists of: phenol 10%～15%, Resorcinol 10%～15%, formaldehyde 55%～65%, urotropine 5%～10%, mass concentration are 40% sodium hydroxide solution 5%～10% and excess water; Above-mentioned per-cent is the weight percent of each ingredients constitute raw material total amount, and each component sum is one of percentage hundred, according to the following steps preparation:
1. the logical water coolant of reaction kettle adds phenol, Resorcinol and mass concentration and is 40% sodium hydroxide solution according to the above ratio in reaction kettle;
2. start stirrer, open cooling water valve, adjustment cooling degree, the control reactor temperature is not higher than 50 ℃;
3. the question response temperature in the kettle no longer raises, when being controlled at below 40 ℃, add urotropine dissolving according to the above ratio after, slowly add formaldehyde again, the control reactor temperature is no more than 50 ℃ during adding;
4. material all adds back stirring reaction 20min～30min, observes that temperature no longer raises and discharging when falling trend is arranged, and promptly gets phenolic resin pre-condensation polymer cross-linking agent;
Through the proportioning of adjustment polymkeric substance 1000mg/L～5000mg/L and linking agent 2000mg/L～15000mg/L, crosslinking time was controlled at 1～30 day, and the frozen glue viscosity of formation is 500mPa.s～100000mPa.s.
2. according to the preparation method of the described phenolic resin pre-condensation polymer cross-linking agent of claim 1, it is characterized in that the ratio of phenol is 11%～13% (wt) in the raw material.
3. according to the preparation method of the described phenolic resin pre-condensation polymer cross-linking agent of claim 1, it is characterized in that the ratio of Resorcinol is 11%～13% (wt) in the raw material.
4. according to the preparation method of the described phenolic resin pre-condensation polymer cross-linking agent of claim 1, it is characterized in that mass concentration is that the ratio of 40% sodium hydroxide solution is 5%～8% (wt) in the raw material.
5. according to the preparation method of the described phenolic resin pre-condensation polymer cross-linking agent of claim 1, it is characterized in that the ratio of formaldehyde is 58%～63% (wt) in the raw material.
6. according to the preparation method of the described phenolic resin pre-condensation polymer cross-linking agent of claim 1, it is characterized in that the ratio of urotropine is 6%～9% (wt) in the raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910231586 CN101735421B (en) | 2009-12-03 | 2009-12-03 | Method for preparing phenolic resin pre-condensation polymer cross-linking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910231586 CN101735421B (en) | 2009-12-03 | 2009-12-03 | Method for preparing phenolic resin pre-condensation polymer cross-linking agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101735421A CN101735421A (en) | 2010-06-16 |
| CN101735421B true CN101735421B (en) | 2012-12-12 |
Family
ID=42459490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910231586 Active CN101735421B (en) | 2009-12-03 | 2009-12-03 | Method for preparing phenolic resin pre-condensation polymer cross-linking agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101735421B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060966A (en) * | 2010-10-29 | 2011-05-18 | 鄯善华油技术服务有限公司 | Synthesis and application in chemical control of HY2008JL high-temperature cross-linking agent |
| CN104498006B (en) * | 2014-12-29 | 2017-10-31 | 中国石油天然气集团公司 | A kind of manufacture method of the manufacture method of crosslinking agent, crosslinking agent and profile control agent |
| CN107057667B (en) * | 2017-04-28 | 2020-04-21 | 中国石油天然气集团公司 | Modified phenolic crosslinking agent and preparation method and application thereof |
| CN110295034B (en) * | 2019-06-18 | 2021-03-09 | 西南石油大学 | Gas injection channeling-preventing agent for deep part of carbonate karst cave or hole oil reservoir and application method thereof |
| CN112094629B (en) * | 2020-09-07 | 2022-08-30 | 中国海洋石油集团有限公司 | Plugging agent suitable for fractured oil reservoir |
| CN112410002B (en) * | 2020-10-21 | 2023-03-07 | 中国石油天然气集团公司 | Cross-linking agent and preparation method thereof, high-temperature delay profile control agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1323776A2 (en) * | 2001-12-20 | 2003-07-02 | Surface Specialties Germany GmbH & Co. KG | Use of plastified novolak resins as additive for rubber mixtures |
| WO2004063259A1 (en) * | 2003-01-16 | 2004-07-29 | Abdeslam Kasseh | Self-foamable organoclay/novolak nanocomposites and process thereof |
-
2009
- 2009-12-03 CN CN 200910231586 patent/CN101735421B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1323776A2 (en) * | 2001-12-20 | 2003-07-02 | Surface Specialties Germany GmbH & Co. KG | Use of plastified novolak resins as additive for rubber mixtures |
| WO2004063259A1 (en) * | 2003-01-16 | 2004-07-29 | Abdeslam Kasseh | Self-foamable organoclay/novolak nanocomposites and process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101735421A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101735421B (en) | Method for preparing phenolic resin pre-condensation polymer cross-linking agent | |
| US4558080A (en) | Stable tannin based polymer compound | |
| JP6588433B2 (en) | Method for treating lignin and producing a binder composition | |
| CN102241826B (en) | Modified lignin and urea-formaldehyde resin synthesized from same and preparation methods of modified lignin and urea-formaldehyde resin | |
| JP2016539216A (en) | Method for treating lignin and for producing a binder composition | |
| JP6905942B2 (en) | Methods for increasing the reactivity of lignin, the resin composition containing the lignin, and the use of the resin composition. | |
| CN103992466B (en) | A kind of planographic ink rosen polyester resin and synthetic method thereof | |
| US2878197A (en) | Thixotropic phenol-aldehyde adhesive composition and method of making same | |
| CN101412796B (en) | Hot melt type phenolic resin modified by using enzymatic hydrolysis lignin or derivatives thereof, and preparation thereof | |
| CN101104782A (en) | Lignin-base auxiliary agent for phenolic resin adhesive and its preparation method and application | |
| CN102875753B (en) | Lignin modified phenolic resin and using method thereof | |
| CN107903365B (en) | Urea phenolic resin cross-linking agent and synthesis method thereof | |
| CN101328252A (en) | Preparation of low free monomer, degradable persimmon tannin modified phenolic resin | |
| US3432453A (en) | De-ionizing treatment for phenolic resins using a soluble ammonium salt | |
| CN102617819B (en) | Production method for dialdehyde starch adhesive | |
| CN112410002B (en) | Cross-linking agent and preparation method thereof, high-temperature delay profile control agent and preparation method thereof | |
| CN106590524B (en) | A kind of sodium tetraborate makees the method that preservative prepares corrosion-resistant soybean albumen adhesive | |
| JP6748736B2 (en) | Incorporation of boron complex into resin | |
| CN101870856B (en) | Bark powder phenolic-resin adhesive and preparation method thereof | |
| CN107099009B (en) | Boric acid/pyrolysis oil is total to the preparation method of modified artificial plate thermosetting phenolic resin | |
| CN106750067A (en) | A kind of preparation method of lignin Cardanol Modified PF Resin | |
| CN106750068A (en) | A kind of preparation method of lignin modification phenolic resin | |
| CN103435765A (en) | Phenolic resin modified by butyronitrile latex and anacardol and preparation technology thereof | |
| JPS6162573A (en) | Tannin adhesive composition | |
| JP2014047257A (en) | Thermosetting lignin composition and method of producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Dai Caili Inventor after: You Qing Inventor after: Zhao Fulin Inventor after: Zhao Guang Inventor after: He Long Inventor before: Dai Caili Inventor before: Zhao Fulin |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: DAI CAILI ZHAO FULIN TO: DAI CAILI YOU QING ZHAO FULIN ZHAO GUANG HE LONG |