CN102181057B - Vinyl-containing organic silicon resin for sand screen and preparation method and application thereof - Google Patents
Vinyl-containing organic silicon resin for sand screen and preparation method and application thereof Download PDFInfo
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- CN102181057B CN102181057B CN2011100747105A CN201110074710A CN102181057B CN 102181057 B CN102181057 B CN 102181057B CN 2011100747105 A CN2011100747105 A CN 2011100747105A CN 201110074710 A CN201110074710 A CN 201110074710A CN 102181057 B CN102181057 B CN 102181057B
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Abstract
The invention relates to vinyl-containing organic silicon resin for a sand screen and a preparation method and application thereof, belonging to the technical field of high polymer materials. The structural generation of the vinyl-containing organic silicon resin is shown in the specification, wherein the molecular weight of the organic silicon resin is 1,000-10,000; m is 60-120; n is 0-80; R1 is methyl, phenyl or vinyl; R2 is methyl, phenyl or vinyl; R3 is methyl, phenyl or vinyl; R1 represents same or different groups; when n is more than or equal to 2, R2 represents same or different groups; and R3 represents same or different groups. Due to the introduction of a vinyl functional group into the organic silicon resin, the flexibility of a high polymer substrate is enhanced, and the organic silicon resin is in a rubber state at normal temperature and has high flexibility; and the organic silicon resin is further crosslinked and becomes crisp under the downhole temperature condition of a horizontal well.
Description
Technical field
The present invention relates to a kind of sand screen with silicone resin that contains vinyl and preparation method thereof and application, belong to technical field of polymer materials.
Background technology
Horizontal well drillable quartz sand filter tube sand-prevention assorted tubing string need to have certain sinuousness when stretching into horizontal well, therefore, connection glue between sleeved need to have certain toughness, but after entering horizontal well, need the fixing sclerosis of this connection glue, thereby reach complete sealing off gap and the convenient purpose of taking out of pulverizing.Such as publication number be: the Chinese patent of CN101343992 discloses a kind of horizontal well drillable quartz sand filter tube sand-prevention assorted tubing string, formed by pkr, quartz sand chimney filter, drillable pipe core, Drillable stabilizer and drillable plug, it is characterized in that the cover tube hub that stretches to oil reservoir at horizontal well arranges a drillable pipe core, direct puncture is crossed the transverse section of sand control oil reservoir, drillable pipe core rear end is provided with pkr, the annular space of packing drillable pipe core and sand string; Front end arranges a drillable plug, and the pipe core cover between pkr and drillable plug has several quartz sand chimney filters, is provided with Drillable stabilizer between the quartz sand chimney filter.This patent just exists does not in use have suitable seal gum, and it is firm or toughness is not good usually to produce gap sealing, and sleeve pipe stretches into the problems such as horizontal well difficulty.Horizontal well technology has the advantages such as the workable reserve of expansion, enhancing degree vapour ability, the used well number of minimizing oil-field development, the application and development of this technology more and more receives people's concern, but its performance requriements to seal gum between the drillable quartz sand filter tube sand-prevention assorted column jacket is harsher.Solution to the problems described above is developed a kind of seal gum exactly, require seal gum at room temperature to have good elasticity, make its easy distortion, thereby enter easily horizontal well, but after entering, reach at horizontal well temperature under 60～80 ℃ the condition, the seal gum sclerosis, toughness drop, fragility improves, this connection glue can conveniently bore brokenly in case sand screen lost efficacy, and was convenient to take out.At present, common seal gum is difficult to satisfy the job requirements of horizontal well thermal production well.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of sand screen with silicone resin that contains vinyl and preparation method thereof and application.The vinyl-functional that this silicone resin is introduced has been strengthened the flexibility of macromolecule matrix, makes under its normal temperature to become rubbery state, and flexible, this machine silicone resin is further crosslinked under the downhole temperature condition of horizontal well, becomes the crisp state of matter.
The sand screen silicone resin that contains vinyl has following general structure:
Wherein, the molecular weight of silicone resin is 1000～10000, and wherein the m value is that 60～120, n value is 0～80, R
1Be methyl, phenyl or vinyl, R
2Be methyl, phenyl or vinyl, R
3Be methyl, phenyl or vinyl, R
1Represent identical or different group; When n 〉=2, R
2Represent identical or different group, R
3Represent identical or different group.
The above-mentioned preparation method who contains the silicone resin of vinyl, step is as follows:
(1) ratio with Union carbide A-162, phenyl triethoxysilane, vinyltriethoxysilane and dialkyl group diethoxy silane 10: 1 in molar ratio～5: 1～5: 1～5 mixes, and gets the raw material mixed solution;
(2) under the condition that cryosel is bathed, drip hydrolysising solvent in the raw material mixed solution that makes to step (1), the reaction 6～8h that is hydrolyzed, then stirring at room is 0.5 hour, after reaction is finished, leaves standstill, carry out separatory after, get upper oil phase, get hydrolyzate;
(3) hydrolyzate that step (2) is made is washed to neutrality, and is dry under the room temperature, then steams except organic solvent, must contain the silicone resin of vinyl.
In the described step (1) the dialkyl group diethoxy silane be selected from one of aminomethyl phenyl diethoxy silane, dimethyldiethoxysilane, methyl ethylene diethoxy silane, phenylbenzene diethoxy silane or arbitrarily than combination.
The ratio of Union carbide A-162, phenyl triethoxysilane, vinyltriethoxysilane and alkyl diethoxy silane 10: 2 in molar ratio～4: 2～4: 1～5 mixes in the described step (1).
Hydrolysising solvent in the described step (2) is that water mixes with organic solvent and makes, and wherein the consumption of water is 5～10 times of mole total amount of alkoxyl group in the raw material mixed solution, and the consumption of organic solvent is long-pending 0.8～1.2 times of starting material liquid mixture.
Organic solvent in the above-mentioned steps (2) be selected from one of benzene,toluene,xylene, chlorobenzene, sherwood oil, naphthenic hydrocarbon, halohydrocarbon, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE or arbitrarily than combination.
The curing process of this vinyl polysiloxane is:
The titanium complex that contains that this vinyl polysiloxane is added 2～10 parts tetraethoxy and 2～8 parts, then add 1～10 part of containing hydrogen silicone oil and contain the chloroplatinic acid catalyst of catalytic inhibitor, stir, then casting, under the room temperature condition, solidified 7 days, and be rubber-like, have good elasticity; Then under 60～80 ℃, further solidified 4 days, cross-linking density further increases, and performance improves, but flexibility decrease, and matter is crisp.
The application that contains the silicone resin of vinyl of the present invention is used for slit between the sealed horizontal well drillable quartz sand filter tube sand-prevention assorted column jacket as seal gum.
The invention has the advantages that:
1. silicone resin of the present invention has been introduced the good vinyl of kindliness, utilizes simultaneously phenyl and vinyl to strengthen its mechanical property.With vinyl trialkyl oxysilane and methyl trialkoxysilane, the phenyl trialkoxy silane is used with, has prepared better performances, the silicon-containing polymer that kindliness is good.
The silicone resin that contains vinyl of the present invention at room temperature one section crosslinked, form the polymer elastomer of low cross-linking, have preferably elasticity, and stronger intensity arranged, satisfy the working conditions of special occasions.When continuing 60～80 ℃ of lower continuously uses, cross-linking density increases, and polymer elasticity descends gradually, and it is large that fragility constantly becomes, so that toughness reduces greatly, is easy to break into pieces.
3. the resin matrix of the silicone resin that contains vinyl of the present invention is in preparation process, do not have the corrosives such as hydrochloric acid to produce, and is less to the organic reagent consumption simultaneously, recoverable, and cost is lower, less pollution.In addition, the resin building-up process is simple, easily preparation, and reaction is easy to control.
Embodiment
Below in conjunction with embodiment the present invention is described further, but institute of the present invention protection domain is not limited to this.
Embodiment 1
With the 820g Union carbide A-162,480g phenyl triethoxysilane and 414g vinyltriethoxysilane and 80g dimethyldiethoxysilane mixing, in cryosel is bathed, slowly add water and the 600ml toluene of 2700g, be added dropwise to complete rear stirring at room 0.5 hour, standing demix, behind the separatory, get upper oil phase, get hydrolyzate, then wash hydrolyzate to neutral, add Calcium Chloride Powder Anhydrous and carry out drying.After the polymkeric substance drying, cross and filter out calcium chloride, then toluene is steamed, namely make the silicone resin that contains vinyl.
Performance measurement:
The silicone resin 40g that will contain vinyl, adding 2g tetraethoxy and 1.2g model is the titanium complex of D-60, with the 2g hydrogen content be 1.4% containing hydrogen silicone oil and chloroplatinic acid catalyst, be positioned in the mould after stirring, middle curing molding at room temperature, one section solidified 7 days, obtained having certain elastic one section cured silicone resin; Then, one section cured silicone resin is positioned over carries out two sections curing in 80 ℃ of baking ovens, further solidified through 4 days, obtain two sections crisp cured silicone resins of matter.Its performance sees Table 1
The performance of table 1 vinyl organosilicon resin
| Tensile strength/MPa | Elongation/% | Hardness (S) | |
| One section cured silicone resin | 3.05 | 140 | 64 |
| Two sections cured silicone resins | 9.05 | 40 | 86 |
Embodiment 2
With the 712g Union carbide A-162,480g phenyl triethoxysilane, 414g vinyltriethoxysilane and 148g methyl ethylene diethoxy silane mixing, in cryosel is bathed, slowly add water and the 500ml toluene of 2340g, after being added dropwise to complete, stirring at room 0.5 hour, standing demix behind the separatory, is got upper oil phase, get hydrolyzate, continue to stir hydrolyzate, then wash hydrolyzate to neutral, add Calcium Chloride Powder Anhydrous and carry out drying.After the polymkeric substance drying, cross and filter out calcium chloride, then toluene is steamed, namely make the silicone resin that contains vinyl.
Performance measurement:
The silicone resin 40g that contains vinyl, adding 2.4g tetraethoxy and 1.6g model is the titanium complex of D-60, with the 2g hydrogen content be 1.4% containing hydrogen silicone oil and chloroplatinic acid catalyst, be positioned in the mould after stirring, middle curing molding at room temperature, one section solidified 7 days, obtained having certain elastic one section cured silicone resin; Then, one section cured silicone resin is positioned over carries out two sections curing in 80 ℃ of baking ovens, further solidified through 4 days, obtain two sections crisp cured silicone resins of matter.Its performance sees Table 2
The performance of table 2 vinyl organosilicon resin
| Tensile strength/MPa | Elongation/% | Hardness (S) | |
| One section cured silicone resin | 3.15 | 190 | 62 |
| Two sections cured silicone resins | 9.65 | 40 | 84 |
Embodiment 3
With the 890g Union carbide A-162,240g phenyl triethoxysilane, 414g vinyltriethoxysilane and 210g aminomethyl phenyl diethoxy silane mixing, in cryosel is bathed, slowly add water and the 500ml toluene of 2340g, after being added dropwise to complete, stirring at room 0.5 hour, standing demix behind the separatory, is got upper oil phase, get hydrolyzate, continue to stir hydrolyzate, then wash hydrolyzate to neutral, add Calcium Chloride Powder Anhydrous and carry out drying.After the polymkeric substance drying, cross and filter out calcium chloride, then toluene is steamed, namely make the silicone resin that contains vinyl.
Performance measurement:
The silicone resin 40g that will contain vinyl, adding 2.8g tetraethoxy and 1.6g model is the titanium complex of D-60, with the 2.4g hydrogen content be 1.4% containing hydrogen silicone oil and chloroplatinic acid catalyst, be positioned in the mould after stirring, middle curing molding at room temperature, one section solidifies 7d, obtains having certain elastic one section cured silicone resin; Then, one section cured silicone resin is positioned over carries out two sections curing in 80 ℃ of baking ovens, further solidified through 4 days, obtain two sections crisp cured silicone resins of matter.Its performance sees Table 3.
The performance of table 3 vinyl organosilicon resin
| Tensile strength/MPa | Elongation/% | Hardness (S) | |
| One section cured silicone resin | 3.55 | 170 | 66 |
| Two sections cured silicone resins | 8.95 | 50 | 84 |
Claims (2)
1. contain the preparation method of the silicone resin of vinyl, it is characterized in that, step is as follows:
(1) with Union carbide A-162, phenyl triethoxysilane, vinyltriethoxysilane and dialkyl group diethoxy silane in molar ratio the ratio of 10:1～5:1～5:1～5 mix, get the raw material mixed solution;
(2) under the condition that cryosel is bathed, drip hydrolysising solvent in the raw material mixed solution that makes to step (1), the reaction 6～8h that is hydrolyzed, then stirring at room is 0.5 hour, after reaction is finished, leaves standstill, carry out separatory after, get upper oil phase, get hydrolyzate;
(3) hydrolyzate that step (2) is made is washed to neutrality, and is dry under the room temperature, then steams except organic solvent, must contain the silicone resin of vinyl, has following general structure:
Wherein, the molecular weight of silicone resin is 1000～10000, and wherein the m value is that 60～120, n value is 0～80, R
1Be methyl, phenyl or vinyl, R
2Be methyl, R
3Be methyl, R
1Represent different groups.
2. preparation method as claimed in claim 1, it is characterized in that the middle Union carbide A-162 of described step (1), phenyl triethoxysilane, vinyltriethoxysilane and dialkyl group the diethoxy silane in molar ratio ratio of 10:2～4:2～4:1～5 mix.
3, preparation method as claimed in claim 1, it is characterized in that, hydrolysising solvent in the described step (2) is that water mixes with organic solvent and makes, wherein the consumption of water is 5～10 times of mole total amount of alkoxyl group in the raw material mixed solution, and the consumption of organic solvent is long-pending 0.8～1.2 times of starting material liquid mixture.
4, preparation method as claimed in claim 3 is characterized in that, the organic solvent in the described step (2) be selected from one of benzene,toluene,xylene, chlorobenzene, sherwood oil, naphthenic hydrocarbon, halohydrocarbon, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE or arbitrarily than combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100747105A CN102181057B (en) | 2011-03-28 | 2011-03-28 | Vinyl-containing organic silicon resin for sand screen and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100747105A CN102181057B (en) | 2011-03-28 | 2011-03-28 | Vinyl-containing organic silicon resin for sand screen and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN102181057A CN102181057A (en) | 2011-09-14 |
| CN102181057B true CN102181057B (en) | 2013-01-02 |
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Granted publication date: 20130102 |