CN103396783B - A kind of resin coated propping agent and preparation method thereof - Google Patents
A kind of resin coated propping agent and preparation method thereof Download PDFInfo
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- CN103396783B CN103396783B CN201310318393.6A CN201310318393A CN103396783B CN 103396783 B CN103396783 B CN 103396783B CN 201310318393 A CN201310318393 A CN 201310318393A CN 103396783 B CN103396783 B CN 103396783B
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- 229920005989 resin Polymers 0.000 title claims abstract description 166
- 239000011347 resin Substances 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 98
- 239000011737 fluorine Substances 0.000 claims abstract description 52
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 52
- 238000004140 cleaning Methods 0.000 claims abstract description 51
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000002708 enhancing effect Effects 0.000 claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 238000000465 moulding Methods 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000007704 transition Effects 0.000 claims abstract description 11
- 229920003986 novolac Polymers 0.000 claims abstract description 9
- 238000005728 strengthening Methods 0.000 claims abstract description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 39
- 229920000768 polyamine Polymers 0.000 claims description 31
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 20
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 20
- 239000007822 coupling agent Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 14
- -1 alkane diamines Chemical class 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 11
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical group CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- XCDAQRPDPPVVEF-UHFFFAOYSA-N N-[diethoxy(prop-2-enoxy)silyl]aniline Chemical compound N(C1=CC=CC=C1)[Si](OCC=C)(OCC)OCC XCDAQRPDPPVVEF-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical group 0.000 claims description 3
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000007711 solidification Methods 0.000 description 22
- 230000008023 solidification Effects 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000006004 Quartz sand Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920003987 resole Polymers 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920001342 Bakelite® Polymers 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004637 bakelite Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention provides a kind of resin coated propping agent and preparation method thereof, resin coated propping agent of the present invention comprise aggregate, strengthen the enhancing resin molding that resin covers at aggregate surface, self-cleaning resin molding that self-cleaning resin covers at aggregate surface and for solving the interface transition layer strengthening interface problem between resin molding and self-cleaning resin molding; Described enhancing resin is selected from epoxy resin and/or novolac resin; Described self-cleaning resin is the fluoro-resin with self-cleaning function, and described interface transition layer adopts organic fluorine modified epoxy.Propping agent of the present invention not only has the characteristic that density is low and intensity is high, and has self-cleaning function.The inventive method is simple, is easy to universal in suitability for industrialized production.
Description
Technical field
The present invention relates to the exploitation of oil, Sweet natural gas and shale gas pressure break field, particularly a kind of resin coated propping agent and preparation method thereof.
Background technology
Fracturing yield increasing is taked to be one of major technique of current oil (gas) field volume increase in transforming shale gas, hyposmosis, ultra-low penetration and old well, propping agent carries feeding formation fracture as the essential material of fracturing yield increasing by fracturing liquid, thus play the effect supporting formation fracture and conduction pathway is provided, make to derive oil, gas well smoothly in oil, the gas gap between propping agent.Therefore, the over-all properties of propping agent decides the oil of Oil/gas Well, gas output affect effective volume increase of Oil/gas Well.
Conventional proppants in the market based in close haydite and quartz sand, in close ceramsite propping agent have higher resistant to breakage ability (52MPa percentage of damage is generally less than 5%), degree of sphericity is good, flow conductivity is strong, but relative density is large, and require that sand-carrying agent viscosity is higher, difficulty of construction is larger, comparatively serious to transferpump and pipe wear, make executive cost and the invisible increase of device security risk; Natural siliceous sand relative density is lower, is convenient to fracturing liquid and carries conveying, but due to its intensity low, compatibly ply stress is lower than the stratum of 35MPa.In real work, technician is at conventional proppants surface coating one deck resin film, be called resin coated propping agent, resin coated propping agent significantly can reduce percentage of damage, turbidity, the acid solubility of propping agent, and the flow conductivity and the prolongation pressure break that improve propping agent are ageing.Therefore, the consumption of resin coated propping agent is increasing gradually.
Chinese patent application 200410001002.9 discloses a kind of resin coating quartz sand, the heat-drawn wire of the resin molding of this resin coating quartz sand is lower, when the heat-drawn wire of formation temperature higher than resin molding, resin molding does not have the effect of dispersive stress to quartz sand; And small molecules softening agent also reduces the water tolerance of resin molding.
Chinese patent application 200910083223.8 discloses one and relates to a kind of functional type precured resin coated propping agent, it comprises aggregate and the resin molding at the outer overlay film of aggregate, described resin molding comprises the silicoorganic compound containing one or more active groups in amino, hydroxyl, carboxyl, alkoxyl group and sulfydryl, after solidification, resin molding has different wetting properties to oil, glassware for drinking water, improve oil gas with the separating effect of water and resistant to breakage ability, long-term water conservancy diversion is effective.Chinese patent application 200910203794.0 discloses one and relates to precured resin coated propping agent, and this proppant strength is high, and has excellent antistatic property and water resistance.Although the resistant to breakage rate of the overlay film propping agent of these two patents after immersion increases, go back Shortcomings, also not there is self-cleaning function simultaneously.
In oil, gas well fracturing stimulation process, in order to reduce the injury of of the fracturing fluid consumption and minimizing fracturing liquid formation, propping agent is required it is that intensity is higher and density is more low better, propping agent density is lower, fracturing liquid is carried to the farther distance of formation fracture, favourable to the flow conductivity improving crack.The low close propping agent can supplied in the market has low-density ceramsite, and (volume density is less than 1.4g/cm
3, be less than 2.50g/cm depending on close
3, 52MPa percentage of damage is greater than 15%) and quartz sand, not only percentage of damage is high for these two kinds of propping agents, and intensity is low; And after pressing crack construction in christmas process, because resident fluid flows for a long time in supporting crack, cause stratum mineral and impurity absorption at haydite and quartz sand surface, the hole between propping agent is caused to reduce even to block, the flow conductivity of man-made fracture is caused to reduce, Oil/gas Well production rate decline is fast, the problem that after pressure break, validity period is shorter.
Therefore, need one at present badly and there is self-cleaning function, and the resin coated propping agent that density is low, intensity is high.
Summary of the invention
According to demand and the deficiency in above-mentioned field, the invention provides a kind of resin coated propping agent, this propping agent not only has the characteristic that density is low and intensity is high, and has self-cleaning function.
Technical scheme of the present invention is as follows:
A kind of resin coated propping agent, it is characterized in that, comprise aggregate, strengthen the enhancing resin molding that resin covers at aggregate surface, self-cleaning resin molding that self-cleaning resin covers at aggregate surface and for solving the interface transition layer strengthening interface problem between resin molding and self-cleaning resin molding; Described enhancing resin is selected from epoxy resin and/or novolac resin; Described self-cleaning resin is the fluoro-resin with self-cleaning function, and described interface transition layer adopts organic fluorine modified epoxy.
Described enhancing resin accounts for 0.5 ~ 6% of aggregate weigh; Described self-cleaning resin accounts for 0.5 ~ 3% of aggregate weigh; Described organic fluorine modified epoxy accounts for 0.1 ~ 2% of aggregate weigh.The propping agent of this ratio not only has self-cleaning function but also has higher intensity, strengthens resin also stronger with the mutual bonding effect between self-cleaning resin simultaneously, and prepares the material cost also decrease to some degree of this propping agent.
Described enhancing resin accounts for 1.5 ~ 3% of aggregate weigh, and described organic fluorine modified epoxy accounts for 0.2 ~ 1% of aggregate weigh.Intensity and the enhancing resin of the propping agent of this proportional range improve further with the mutual bonding effect between self-cleaning resin, and the cost of material reduces further.
When described enhancing resin is bisphenol A-type and/or bisphenol F epoxy resin;
Solidifying agent used is selected from alicyclic polyamine, aromatic polyamine, modified alliphatic polyamine and/or modified aromatic polyamine, and the consumption of solidifying agent accounts for 10 ~ 40% of weight epoxy;
Described alicyclic polyamine be selected from isophorone diamine, two aminocyclohexane, diamino-dicyclohexyl methane, adjacent diamines methylcyclopentane and the Meng alkane diamines; Described aromatic polyamine is selected from mphenylenediamine, diaminodiphenyl-methane; Described modified alicyclic polyamine or modified aromatic polyamine are 1mol polyamine and 0.05 ~ 0.3mol phenyl glycidyl ether or the reaction product of cresylol glycidyl ether at 30 ~ 70 DEG C.
When described enhancing resin is novolac resin, solidifying agent used is hexamethylenetetramine, and solidifying agent accounts for 10 ~ 20% of phenolic resin weight.
Described fluoro-resin is selected from solvent-based two-component fluorocarbon coating resin, normal temperature cured type tetrafluoro resin, aircraft series F-C paint, steel construction series F-C paint, petrochemical complex series F-C paint.
Described organic fluorine modified epoxy is selected from organic fluorine modified bisphenol A type epoxy resin, organic fluorine modified bisphenol F epoxy resin.
The preparation method of above-mentioned propping agent, comprises the steps:
1) heated by aggregate, under agitation add the enhancing resin containing coupling agent, make enhancing resin coating on aggregate, then add solidifying agent and be cured, described coupling agent accounts for and strengthens 0.5 ~ 2% of weight resin;
2) add fluorine richness epoxy resin and stir, adding epoxy curing agent and be cured;
3) add the organic fluorine mixed in advance and solidifying agent and stir and be cured;
4) material is cooled, broken and sieve.
Method of modifying in described fluorine richness epoxy resin is use an isocyanate group of diisocyanate cpd with the hydroxyl reaction of epoxy resin self, and another isocyanate group is reacted with the fluorine cpd with hydroxyl.
Described coupling agent is silane coupling agent, be selected from γ-aminopropyl triethoxysilane, N, N-two (beta-hydroxyethyl)-γ-aminocarbonyl propyl trimethoxy silane, anilino methylene triethoxyl silane, γ mercaptopropyitrimethoxy silane, γ-glycidyl ether propyl trimethoxy silicane; Described coupling agent is 0.1 ~ 3:100 with the ratio of enhancing weight resin.The selection of described coupling agent and proportioning can well strengthen resin with the cohesive strength between aggregate.
Described coupling agent is 0.5 ~ 2:100 with the ratio of enhancing weight resin.Coupling agent and the enhancing resin of this proportioning can strengthen resin further with the cohesive strength between aggregate.
In order to improve the intensity of propping agent, with epoxy resin and novolac resin to aggregate overlay film, ensure the intensity of propping agent.Described resin accounts for 0.5 ~ 6% of aggregate weigh, and this ratio can strengthen the intensity of propping agent, preferably 1.5 ~ 3%, the intensity of the propping agent of this quantity resin improve further and also cost also lower.
Further, when enhancing resin of the present invention is epoxy resin, the oxirane value of resin used is greater than 0.10 mole/100 grams; When enhancing resin of the present invention is novolac resin, the softening temperature of resin used is greater than 80 DEG C, and 150 DEG C of rates of polymerization are less than 120 seconds, and free phenol content is less than 0.5%, the enhancing resin meeting above-mentioned condition meets environmental requirement, and can meet good overlay film performance.
Further, in resin coated propping agent of the present invention, when described enhancing resin is epoxy resin, solidifying agent is organic polyamine class, and described epoxy curing agent is alicyclic polyamine, aromatic polyamine, modified alliphatic polyamine and/or modified aromatic polyamine.Alicyclic polyamine is as one or more in isophorone diamine, two aminocyclohexane, diamino-dicyclohexyl methane, adjacent diamines methylcyclopentane and Meng alkane diamines; Aromatic polyamine as mphenylenediamine, diaminodiphenyl-methane; Modified cycloaliphatic or aromatic polyamine are preferably the aforesaid alicyclic and aromatic polyamine of 1mol and 0.05 ~ 0.3mol is selected from the reaction product at 30 ~ 70 DEG C by epoxy resin diluent phenyl glycidyl ether or cresylol glycidyl ether.The consumption of described solidifying agent accounts for pre-overlay film strengthens weight resin 10 ~ 40%.
When described resin is novolac resin, solidifying agent is hexamethylenetetramine, and consumption accounts for 10 ~ 20% of phenolic resin weight.The solidifying agent of this ratio can make novolac resin film strength well be strengthened.
In order to overcome strengthen resin molding with between self-cleaning resin molding due to cohesive strength more weak and produce interface problem, the present invention adopts organic fluorine modified epoxy to make interface transition layer, and consumption accounts for 0.1 ~ 2% of aggregate weigh, and optimum consumption is 0.5 ~ 1%.Organic fluorine modified epoxy comprise organic fluorine richness bisphenol A type epoxy resin, organic fluorine modified bisphenol F epoxy resin one or more, the oxirane value of epoxy resin used is greater than 0.4 mole/100 grams.Method of modifying is use the hydroxyl of epoxy resin self with an isocyanic ester radical reaction of diisocyanate cpd, and another cyanate ester based same fluorine cpd with hydroxyl react.Organic fluorine modified epoxy can well solve and strengthen the problem of resin with bonding strength difference mutual between self-cleaning fluoro-resin.Organic fluorine modified epoxy in the present invention also can use the approach that is purchased to obtain.Described diisocyanate cpd is for comprising phenylene diisocyanate, tolylene diisocyanate, ditolyl methane vulcabond, ethylbenzene vulcabond, cyclohexyl diisocyanate, isophorone diisocyanate.Described hydroxyl fluorine cpd are for comprising but not limitting C3-Fluoroalcohol, hexafluoroisopropanol, octafluoropentanol, ten difluoro enanthol, ten hexafluoro nonyl alcohols.
The method that organofluorine compound is grafted on epoxy resin by described isocyanic ester is the well-known ordinary method of the art: with reference to Wang Chengzhong, Zuo Yu, the synthesis and characteries research of fluorine-containing epoxy resin, thermosetting resin, 2009,24(1) 10 ~ 16, by literature synthesis fluorine richness epoxy resin A.
Further, in the preparation method of overlay film propping agent of the present invention, in order to improve the bonding strength of resin with aggregate, preferably use silane coupling agent.Wherein silane coupling agent is as: γ-aminopropyl triethoxysilane, N, N-two (beta-hydroxyethyl)-γ-aminocarbonyl propyl trimethoxy silane, anilino methylene triethoxyl silane, γ-glycidyl ether propyl trimethoxy silicanes etc.; Coupling agent is 0.1 ~ 3:100 with the ratio of enhancing weight resin, and the proportioning of this coupling agent can well strengthen resin with the cohesive strength between aggregate, and preferred ratio is 0.5 ~ 2:100.
The present invention's self-cleaning resin used is the fluoro-resin with self-cleaning function, as FEM-301 solvent-based two-component fluorocarbon coating resin, FEM-801 normal temperature cured type tetrafluoro coating resin that Zhonglian Fuman Technology (Beijing) Co., Ltd. produces, the aircraft series F-C paint that Dalian Bo Tai fluorine Materials Co., Ltd produces, steel construction series F-C paint, petrochemical complex series F-C paint etc. have the fluoro-resin of self-cleaning characteristic, and preferred self-cleaning resin demand accounts for 0.5 ~ 3% of aggregate weigh.
Further, in the preparation method of propping agent of the present invention, aggregate is heated between 210 ~ 300 DEG C in preferred described step 1, then lower the temperature, the time adding the enhancing resin agitating containing coupling agent when temperature reduces to 200 ± 20 DEG C is 50 ± 10 seconds, enhancing resin can be made fully to mix with coupling agent, strengthen strengthening the cohesive action between resin and aggregate, cause overlay film evenly firm, adding the time that solidifying agent is cured is 90 ± 30 seconds, not only ensure to strengthen resin solidification completely and also resin molding also can not wear and tear; Step 2) in add fluorine richness epoxy resin stir time be 50 ± 10 seconds, adding the time that solidifying agent is cured is 90 ± 30 seconds, the selection of churning time can enable fluorine richness epoxy resin be coated on the outside surface strengthening resin molding uniformly, set time preferably not only ensure fluorine richness epoxy resin cure completely and also resin molding also can not wear and tear.The time adding organic fluorine stirring solidification in step 3) is 180 ± 40 seconds, organic fluorine can be made to be coated on the outside surface of interface transition layer uniformly, and the while of also ensureing that organic fluorine completion of cure and resin molding also can not wear and tear, production efficiency is improved.In addition, first heat up and lower the temperature afterwards, high temperature can remove moisture and a small amount of impurity in aggregate, and then drops to the temperature met, and this operation can also strengthen overlay film intensity.
Preferably, aggregate is heated between 240 ~ 260 DEG C in described step 1), then lower the temperature, add enhancing resin containing coupling agent and the time of stirring is 40 ~ 50 seconds when temperature reduces to 200 ~ 210 DEG C, adding the time that solidifying agent is cured is 60 ~ 90 seconds; Step 2) in add the time that fluorine richness epoxy resin stirs be 40 ~ 50 seconds, adding the time that solidifying agent is cured is 60 ~ 90 seconds; Add organic fluorine in step 3) and stir after fixing 150 ~ 160 seconds.The preferred object of temperature of this heating and cooling program is to make the proppant strength of overlay film further be promoted.In addition, the outside surface of core that each preferred step combined factors gets up to make resin to be coated on core uniformly or to be wrapped by, also ensure resin solidification completely and also resin molding production efficiency simultaneously of also can not wearing and tearing be further enhanced.
Further, in the preparation method of propping agent of the present invention, when described enhancing resin is thermoplastic's resol (such as can buy from Shandong Shengquan Chemical Industry Co., Ltd. and Nantong Sumitomo Bakelite company limited etc.), preferred consolidation agent is hexamethylenetetramine; When described resin is bisphenol A type epoxy resin (such as can buy from Ba Ling petrochemical complex limited liability company, Langfang Nore letter Chemical Co., Ltd. etc.), preferred consolidation agent is alicyclic polyamine and aromatic polyamine, modified alliphatic polyamine and/or modified aromatic polyamine.
The innermost layer of propping agent of the present invention is aggregate, the preferred quartz sand of described aggregate or low close haydite, the self-cleaning resin molding that the enhancing resin molding that this propping agent is from inside to outside followed successively by aggregate, enhancing resin covers at aggregate surface, interface transition layer, self-cleaning resin cover at aggregate surface.The enhancing resin layer of coated aggregate provides intensity guarantee for resin coated propping agent of the present invention, and self-cleaning resin layer can ensure the self-cleaning function of resin coated propping agent, interface transition layer is then equivalent to coupling agent, playing bonding strengthen resin layer with the function served as bridge between self-cleaning resin layer, solve strengthen resin layer with self-cleaning resin layer due to cohesive action more weak and produce interface problem.The technical problem to be solved in the present invention is for the low defect of above-mentioned aggregate (low close haydite and quartz sand) self-strength and surface adsorption problem in the earth formation, a kind of resin coated propping agent is provided, this propping agent not only has the characteristic that density is low and intensity is high, and has self-cleaning function.The inventive method is simple, is easy to universal in suitability for industrialized production.
The technical scheme that the present invention takes beneficial effect is compared with prior art: overlay film propping agent has that intensity is high, density is little and self-cleaning function.
Embodiment
Following embodiment is provided to be to understand the present invention further better; be not limited to described preferred forms; content of the present invention and protection domain are not construed as limiting; anyone is under enlightenment of the present invention or any and the present invention the present invention being carried out combining with the feature of other prior aries and draw is identical or akin product, all drops within protection scope of the present invention.
The present invention's aggregate used is that (volume density is less than 1.4g/cm to low close haydite
3, volume density is less than 2.5g/cm
3) and quartz sand particle, the particle diameter of particle is 1180/850 μm (16/20 order), 1180/600 μm (16/30 order), 850/425 μm (20/40 order), 600/300 μm (30/50 order) and 425/212 μm (40/70 order), and size distribution meets rower SY/T5108-2006.
The source of agents useful for same of the present invention:
FEM-301 solvent-based two-component fluorocarbon coating resin, normal temperature cured type tetrafluoro coating resin FEM-801; Be Zhonglian Fuman Technology (Beijing) Co., Ltd. to produce; Aircraft series F-C paint, steel construction series F-C paint, petrochemical complex series F-C paint are Dalian Bo Tai fluorine Materials Co., Ltd and produce;
Thermoplastic's resol is selected from the product being available commercially from Shandong Shengquan Chemical Industry Co., Ltd. or Nantong Sumitomo Bakelite company limited;
Bisphenol A type epoxy resin, specifications and models are CYD-128 epoxy resin, be available commercially from Ba Ling petrochemical complex limited liability company; Bisphenol f type epoxy resin, is available commercially from Hunan Tuo Suo Science and Technology Ltd..
The preparation method of the organic fluorine modified epoxy in the present invention is the well-known ordinary method of the art, concrete with reference to Wang Chengzhong, Zuo Yu, the synthesis and characteries research of fluorine-containing epoxy resin, thermosetting resin, 2009,24(1) 10 ~ 16, by literature synthesis fluorine richness epoxy resin A; The organic fluorine modified epoxy that the present invention simultaneously also can adopt the approach that is purchased to obtain.
Unreceipted concrete technology or condition person in various embodiments of the present invention, carry out according to the routine techniques described by the document in this area or condition.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional reagent product of commercial acquisition.
Embodiment 1
Be put into self-control sand mill after the quartz sand of 850/425 μm (20/40 order) is heated to 260 DEG C to stir by 3 kilograms of particle diameters, add epoxy resin 60 grams (containing the γ-glycidyl ether propyl trimethoxy silicane of 1% in resin) after being cooled to 200 DEG C and stir 40 seconds, add diaminodiphenyl-methane 15 grams and stir solidification 60 seconds; Add fluorine richness epoxy resin A30 gram to stir 40 seconds, add diaminodiphenyl-methane 4.5 grams and stir solidification 60 seconds; Add solvent-based two-component fluorocarbon coating resin 30 grams solidification 150 seconds, cool, sieve, self-cleaning high-intensity resin overlay film propping agent can be obtained.
Embodiment 2(comparative example)
Be put into self-control sand mill after the quartz sand of 850/425 μm (20/40 order) is heated to 260 DEG C to stir by 3 kilograms of particle diameters, add epoxy resin 60 grams (containing the γ-glycidyl ether propyl trimethoxy silicane of 1% in resin) after being cooled to 200 DEG C and stir 40 seconds, add diaminodiphenyl-methane 15 grams and stir solidification 60 seconds; Add epoxy resin 30 grams to stir 40 seconds, add diaminodiphenyl-methane 7.5 grams and stir solidification 30 seconds; Add calcium stearate 2 grams solidification 150 seconds, cool, sieve, high-intensity resin overlay film propping agent can be obtained.
Table 1. embodiment 1,2 Comparative result
Embodiment 3
Be low close haydite (production of Pingxiang City hundred million prosperous high-tech pottery company limited, the volume density 1.35g/cm of 850/425 μm (20/40 order) by 3 kilograms of particle diameters
3, volume density 2.38g/cm
3) be heated to 250 DEG C after put into self-control sand mill stir, add 90 grams, resol (containing the γ-aminopropyl triethoxysilane of 0.5% in resin) after being cooled to 200 DEG C and stir 45 seconds, add the hexamethylenetetramine aqueous solution (hexamethylenetetramine is 1:2 with water weight ratio) 42 grams and stir solidification 80 seconds; Add fluorine richness epoxy resin A20 gram to stir 45 seconds, add diaminodiphenyl-methane 4 grams and stir solidification 70 seconds; Add BTF-04-GA-2 formed steel construction F-C paint (in advance by component A 30 grams and B component 3 grams mixing) 33 grams of solidifications 160 seconds, cool, sieve, self-cleaning high-intensity resin overlay film propping agent can be obtained.
Embodiment 4(comparative example)
Be put into self-control sand mill after the above-mentioned low close haydite of 850/425 μm (20/40 order) is heated to 250 DEG C to stir by 3 kilograms of particle diameters, add 90 grams, resol (containing the γ-aminopropyl triethoxysilane of 0.5% in resin) after being cooled to 200 DEG C and stir 45 seconds, add the hexamethylenetetramine aqueous solution (hexamethylenetetramine is 1:2 with water weight ratio) 42 grams and stir solidification 80 seconds; Add fluorine richness epoxy resin A20 gram to stir 45 seconds, add diaminodiphenyl-methane 4 grams and stir solidification 30 seconds; Add calcium stearate 2 grams solidification 160 seconds, cool, sieve, high-intensity resin overlay film propping agent can be obtained.
Table 2. embodiment 3,4 Comparative result
Embodiment 5
Be low close haydite (production of Inner Mongol Yu Jia Industrial Co., Ltd., the volume density 1.32g/cm of 425/212 μm (40/70 order) by 3 kilograms of particle diameters
3, volume density 2.37g/cm
3) be heated to 240 DEG C after put into self-control sand mill stir, add 75 grams, resol (containing the γ-aminopropyl triethoxysilane of 0.5% in resin) after being cooled to 210 DEG C and stir 50 seconds, add the hexamethylenetetramine aqueous solution (hexamethylenetetramine is 1:2 with water weight ratio) 36 grams and stir solidification 90 seconds; Add fluorine richness epoxy resin A25 gram to stir 50 seconds, add diaminodiphenyl-methane 5 grams and stir solidification 90 seconds; Add BTF-04-FJ-1 type aircraft F-C paint (in advance by component A 30 grams and B component 3 grams mixing) 33 grams of grams of solidifications 150 seconds, cool, sieve, self-cleaning high-intensity resin overlay film propping agent can be obtained.
Embodiment 6(comparative example)
Be put into self-control sand mill after the above-mentioned low close haydite of 425/212 μm (40/70 order) is heated to 240 DEG C to stir by 3 kilograms of particle diameters, add 75 grams, resol (containing the γ-aminopropyl triethoxysilane of 0.5% in resin) after being cooled to 210 DEG C and stir 50 seconds, add the hexamethylenetetramine aqueous solution (hexamethylenetetramine is 1:2 with water weight ratio) 36 grams and stir solidification 90 seconds; Add fluorine richness epoxy resin 25 grams to stir 60 seconds, add diaminodiphenyl-methane 5 grams and stir solidification 30 seconds; Add calcium stearate 2 grams solidification 180 seconds, cool, sieve, high-intensity resin overlay film propping agent can be obtained.
Table 3. embodiment 5,6 Comparative result
Embodiment 7,8,9,10,11,12,13,14
The preparation method of embodiment 7,8,9,10,11 with embodiment 1, the preparation method of embodiment 13,14 with embodiment 3, the quartz sand simultaneously used in following each embodiment and haydite respectively with embodiment 1, identical in 3; Embodiment 7,8,9,10,11,13,14 use reagent and each reagent dosage as table 4:
Table 4. embodiment 7,8,9,10,11,12,13,14 propping agent agents useful for same and consumption
In table 4, in embodiment 13 and embodiment 14, hexamethylenetetramine 10g/30g and hexamethylenetetramine 16g/48g refers in the hexamethylenetetramine aqueous solution (hexamethylenetetramine is 1:2 with water weight ratio) 30g respectively containing hexamethylenetetramine 10g; And containing hexamethylenetetramine 16g in the hexamethylenetetramine aqueous solution (hexamethylenetetramine is 1:2 with water weight ratio) 48g.
Table 5. embodiment 7,8,9,10,11,12 propping agent capabilities list
As can be seen from above each embodiment, enhancing resin used, self-cleaning resin accounts for aggregate, as long as the consumption of organic fluorine modified epoxy can meet the intensity of resin coated propping agent of the present invention and the requirement of self-cleaning function substantially higher than a minimum value, can realize goal of the invention of the present invention, this minimum value is: strengthen resin and account for 0.5% of aggregate weigh; Self-cleaning resin accounts for 0.5% of aggregate weigh; Organic fluorine modified epoxy accounts for 0.1% of aggregate weigh.In addition, along with the rising of corresponding function resin ratio, the respective performances of obtained resin coated propping agent is also better, but owing to will consider the problem of production cost simultaneously, so the consumption preparing each composition of propping agent is limited in the substantially realistic needs of a maximum value, this maximum value is: strengthen resin and account for 6% of aggregate weigh; Self-cleaning resin accounts for 3% of aggregate weigh; Organic fluorine modified epoxy accounts for 2% of aggregate weigh.And consider the factor coming two aspects, preferably enhancing resin being accounted for aggregate weigh is defined as 1.5 ~ 3%, and self-cleaning resin accounts for aggregate weigh and is defined as 0.5 ~ 3%; Organic fluorine modified epoxy accounts for aggregate weigh and is defined as 0.2 ~ 1% best results.
Embodiment 15. comparative example
The propping agent of the embodiment of the present invention 1 and application number propping agent effectiveness comparison disclosed in 200910203794.0 Chinese invention patent applications
X1 is the propping agent that inventor prepares for preparation method disclosed in 200910203794.0 Chinese invention patent application embodiments 2 and reagent dosage according to application number
The propping agent of X1 and the propping agent of embodiment 1 compare as table 6 in resistant to breakage ability and self-cleaning function:
The table propping agent of 6.X1 compares with the resistant to breakage ability of the propping agent of embodiment 1 and self-cleaning function
As can be seen from Table 6, the resistant to breakage ability of propping agent of the present invention and self-cleaning function are all obviously better than the propping agent that application number is prepared for preparation method disclosed in 200910203794.0 Chinese invention patent application embodiments 2 and reagent dosage.
Claims (5)
1. a resin coated propping agent, it is characterized in that, comprise aggregate, strengthen the enhancing resin molding that resin covers at aggregate surface, self-cleaning resin molding that self-cleaning resin covers at aggregate surface and for solving the interface transition layer strengthening interface problem between resin molding and self-cleaning resin molding; Described enhancing resin is selected from epoxy resin and/or novolac resin; Described self-cleaning resin is the fluoro-resin with self-cleaning function, described interface transition layer adopts organic fluorine modified epoxy, the self-cleaning resin molding that the enhancing resin molding that described propping agent is from inside to outside followed successively by aggregate, enhancing resin covers at aggregate surface, interface transition layer, self-cleaning resin cover at aggregate surface;
Described enhancing resin accounts for 0.5 ~ 6% of aggregate weigh, and described self-cleaning resin accounts for 0.5 ~ 3% of aggregate weigh, and described organic fluorine modified epoxy accounts for 0.1 ~ 2% of aggregate weigh;
When described enhancing resin be bisphenol A-type and/or bisphenol F epoxy resin time, solidifying agent used is selected from alicyclic polyamine, aromatic polyamine, modified alliphatic polyamine and/or modified aromatic polyamine, the consumption of solidifying agent accounts for 10 ~ 40% of weight epoxy, described alicyclic polyamine is selected from isophorone diamine, two aminocyclohexane, diamino-dicyclohexyl methane, adjacent diamines methylcyclopentane and the Meng alkane diamines, described aromatic polyamine is selected from mphenylenediamine, diaminodiphenyl-methane, described modified alicyclic polyamine or modified aromatic polyamine are the product that 1mol polyamine and 0.05 ~ 0.3mol phenyl glycidyl ether or cresylol glycidyl ether react at 30 ~ 70 DEG C,
When described enhancing resin is novolac resin, solidifying agent used is hexamethylenetetramine, and solidifying agent accounts for 10 ~ 20% of phenolic resin weight; Described fluoro-resin is selected from solvent-based two-component fluorocarbon coating resin, normal temperature cured type tetrafluoro resin, aircraft series F-C paint, steel construction series F-C paint, petrochemical complex series F-C paint; Described organic fluorine modified epoxy is selected from organic fluorine modified bisphenol A type epoxy resin, organic fluorine modified bisphenol F epoxy resin.
2. propping agent according to claim 1, is characterized in that, described enhancing resin accounts for 1.5 ~ 3% of aggregate weigh, and described organic fluorine modified epoxy accounts for 0.2 ~ 1% of aggregate weigh.
3. the preparation method of the propping agent described in claim 1 or 2, is characterized in that, comprises the steps:
1) heated by aggregate, under agitation add the enhancing resin containing coupling agent, make enhancing resin coating on aggregate, then add solidifying agent and be cured, described coupling agent accounts for and strengthens 0.5 ~ 2% of weight resin;
2) add organic fluorine modified epoxy and stir, adding epoxy curing agent and be cured;
3) add the fluoro-resin mixed in advance and solidifying agent and stir and be cured;
4) material is cooled, broken and sieve.
4. method according to claim 3, it is characterized in that, method of modifying in described fluorine richness epoxy resin is use an isocyanate group of diisocyanate cpd with the hydroxyl reaction of epoxy resin self, and another isocyanate group is reacted with the fluorine cpd with hydroxyl.
5. want the method described in 3 or 4 according to right, it is characterized in that, described coupling agent is silane coupling agent, be selected from γ-aminopropyl triethoxysilane, N, N-two (beta-hydroxyethyl)-γ-aminocarbonyl propyl trimethoxy silane, anilino methylene triethoxyl silane, γ mercaptopropyitrimethoxy silane, γ-glycidyl ether propyl trimethoxy silicane.
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| CN114479823B (en) * | 2021-12-31 | 2023-06-20 | 宁波锋成先进能源材料研究院有限公司 | Fracturing propping agent and preparation method and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5157077A (en) * | 1990-04-27 | 1992-10-20 | The B. F. Goodrich Company | Epoxy resin systems modified with statistical monofunctional reactive polymers |
| CN1659020A (en) * | 2002-06-03 | 2005-08-24 | 博登化学公司 | Particulate material having multiple curable coatings and methods for making and using same |
| WO2007039758A1 (en) * | 2005-10-06 | 2007-04-12 | Halliburton Energy Services, Inc. | Methods for enhancing aqueous fluid recovery from subterranean formations |
| CN1984769A (en) * | 2004-04-12 | 2007-06-20 | 卡博陶粒有限公司 | Coating and/or treating hydraulic fracturing proppants to improve wettability, proppant lubrication, and/or to reduce damage by fracturing fluids and reservoir fluids |
| CN101608050A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院化学研究所 | Has epoxy resin modified material of three-decker and preparation method thereof |
| CN102660245A (en) * | 2012-03-31 | 2012-09-12 | 北京奇想达科技有限公司 | Pre-coated film propping agent, preparation method of the pre-coated film propping agent and sand prevention method adopting the pre-coated film propping agent |
| CN103131406A (en) * | 2011-11-23 | 2013-06-05 | 中国石油化工股份有限公司 | Super-hydrophobic propping agent and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8944164B2 (en) * | 2011-09-28 | 2015-02-03 | Clearwater International Llc | Aggregating reagents and methods for making and using same |
-
2013
- 2013-07-26 CN CN201310318393.6A patent/CN103396783B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5157077A (en) * | 1990-04-27 | 1992-10-20 | The B. F. Goodrich Company | Epoxy resin systems modified with statistical monofunctional reactive polymers |
| CN1659020A (en) * | 2002-06-03 | 2005-08-24 | 博登化学公司 | Particulate material having multiple curable coatings and methods for making and using same |
| CN1984769A (en) * | 2004-04-12 | 2007-06-20 | 卡博陶粒有限公司 | Coating and/or treating hydraulic fracturing proppants to improve wettability, proppant lubrication, and/or to reduce damage by fracturing fluids and reservoir fluids |
| WO2007039758A1 (en) * | 2005-10-06 | 2007-04-12 | Halliburton Energy Services, Inc. | Methods for enhancing aqueous fluid recovery from subterranean formations |
| CN101608050A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院化学研究所 | Has epoxy resin modified material of three-decker and preparation method thereof |
| CN103131406A (en) * | 2011-11-23 | 2013-06-05 | 中国石油化工股份有限公司 | Super-hydrophobic propping agent and preparation method |
| CN102660245A (en) * | 2012-03-31 | 2012-09-12 | 北京奇想达科技有限公司 | Pre-coated film propping agent, preparation method of the pre-coated film propping agent and sand prevention method adopting the pre-coated film propping agent |
Non-Patent Citations (2)
| Title |
|---|
| 控制支撑剂回流技术新进展;辛军等;《断块油气田》;20080925;第15卷(第05期);99-102 * |
| 树脂覆膜支撑剂研究进展;张伟民等;《热固性树脂》;20111130;第26卷(第06期);55-59 * |
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Inventor after: Zhang Weimin Inventor after: Zhu Yonggang Inventor after: Li Zhangang Inventor after: Meng Chuanyou Inventor after: Ma Xiaojuan Inventor after: Zhao Mengyun Inventor after: Zhang Suobing Inventor after: Chen Li Inventor before: Zhang Weimin Inventor before: Zhu Yonggang Inventor before: Li Zhangang Inventor before: Meng Chuanyou Inventor before: Ma Xiaojuan |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG WEIMIN ZHU YONGGANG LI ZHANGANG MENG CHUANYOU MA XIAOJUAN TO: ZHANG WEIMIN ZHU YONGGANG LI ZHANGANG MENG CHUANYOU MA XIAOJUAN ZHAO MENGYUN ZHANG SUOBING CHEN LI |
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Address after: 100085, Beijing, Haidian District Qinghe Anning East Road No. 2 office building 501, room 18 Co-patentee after: Yangquan golden mean innovation Material Co.,Ltd. Patentee after: BEIJING QISINTAL SCIENCE & TECH Co.,Ltd. Address before: 100085, Beijing, Haidian District Qinghe Anning East Road No. 2 office building 501, room 18 Co-patentee before: YANGQUAN ZHONGYONG CERAMIC PROPPANT Co.,Ltd. Patentee before: BEIJING QISINTAL SCIENCE & TECH Co.,Ltd. |
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Effective date of registration: 20170509 Address after: 100085, room 2, building 18, No. 501, Anning East Road, Beijing, Haidian District Patentee after: BEIJING QISINTAL NEW MATERIAL Co.,Ltd. Address before: 100085, Beijing, Haidian District Qinghe Anning East Road No. 2 office building 501, room 18 Co-patentee before: Yangquan golden mean innovation Material Co.,Ltd. Patentee before: BEIJING QISINTAL SCIENCE & TECH Co.,Ltd. |
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Inventor after: Zhang Weimin Inventor after: Zhu Yonggang Inventor after: Li Zhangang Inventor after: Ma Xiaojuan Inventor after: Zhao Mengyun Inventor after: Zhang Suobing Inventor after: Chen Li Inventor before: Zhang Weimin Inventor before: Zhu Yonggang Inventor before: Li Zhangang Inventor before: Meng Chuanyou Inventor before: Ma Xiaojuan Inventor before: Zhao Mengyun Inventor before: Zhang Suobing Inventor before: Chen Li |
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