CN102321243A - Thioxanthone modified polyethylene imine light initiating agent - Google Patents
Thioxanthone modified polyethylene imine light initiating agent Download PDFInfo
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Abstract
The invention discloses a thioxanthone modified polyethylene imine light initiating agent showed as a formula (I). The thioxanthone modified polyethylene imine is prepared according to a method comprising the following steps of reacting 2-epoxy propoxy thioxanthone with polyethylene imine in a solvent and then obtaining the thioxanthone modified polyethylene imine. The light initiating agent provided by the invention can be used for preparing a start-type acrylamide polymer showed as a formula (II) by an initiate polymerization, wherein a nuclear A represents the thioxanthone modified polyethylene imine showed as a formula (I); an arm B represents an acrylamide homopolymer or a copolymer formed from acrylamide and a comonomer; the molar ratio of the comonomer and the acrylamide is 0.3-0.6 percent. The water-soluble thioxanthone-terminated polyethylene imine light initiating agent provided by the invention has a dendritic structure and a higher light initiating property, and has a greater practical significance on a practical three-dimensional polymer preparation through a light-initiating water solution polyreaction.
Description
Technical field
The present invention relates to a kind of thioxanthone modified polyethyleneimine light trigger.
Background technology
The method for preparing at present star polymer has ATRP, reversible addition-fracture chain transfer polymerization and ring-opening polymerization etc. usually; But these method reaction conditionss require harsh; The polymkeric substance that makes also is generally the star polymer of oil soluble, narrow molecular weight distribution, small molecular weight, and is not suitable for preparing good water solubility, polymkeric substance that molecular weight is big.Light-initiated radical polymerization also can be used to prepare star polymer, and this method reaction conditions is gentle, only needs multi-functional light trigger just can under suitable condition, make star polymer.Among the patent CN1594369 Vestolen PP 7052 has been obtained the dendroid thioxanthone photo initiator after imine modified; Utilize light-initiated radical polymerization to be combined in the mixed solvent of water and DMSO 99.8MIN. and prepared tree nuclear star type SEPIGEL 305; But because the dendroid thioxanthone photo initiator after the modification is water-soluble relatively poor; And be reflected in the mixed solvent and carry out, its molecular weight of product is less.Raw materials used Vestolen PP 7052 imines does not have industrial goods at present in the initiator simultaneously, and cost is high, is unfavorable for industrial production.In order to obtain the light trigger that high-molecular weight star SEPIGEL 305 is necessary to research and develop water-soluble good, polyfunctional group, wide material sources.
Summary of the invention
The purpose of this invention is to provide a kind of thioxanthone modified polyethyleneimine light trigger.
A kind of thioxanthone modified polyethyleneimine light trigger provided by the invention, its structural formula are suc as formula (I):
Polymerization degree N=1-16 wherein.
In the above-mentioned thioxanthone modified polyethyleneimine, said polymerization degree N can be 1-6,3-6,1,3,6 or 16.
Above-mentioned thioxanthone modified polyethyleneimine can prepare according to the method that comprises the steps: 2-glycidoxy thioxanthone and polymine react in solvent and promptly get product; The polymerization degree of said polymine can be 1-16, specifically can be 1-6,3-6,1,3,6 or 16; Weight-average molecular weight Mw can be 600g/mol-10000g/mol;
The ratio of quality and the number of copies of said 2-glycidoxy thioxanthone and said polymine can be 5: 2; Said solvent can be chloroform, thionyl chloride, N, dinethylformamide or dithiocarbonic anhydride; The time of said reaction can be 16 hours-36 hours; The temperature of said reaction can be 40 ℃-70 ℃.
Thioxanthone modified polyethyleneimine light trigger provided by the invention can be used for initiated polymerization and prepares the star-like SEPIGEL 305 base polymer of polymine shown in the formula (II) for nuclear.
Wherein, nuclear A is thioxanthone modified polyethyleneimine shown in the formula (I), wherein polymerization degree N=1-16; Arm B is methacrylamide homopolymer or the multipolymer that formed by acrylic amide and comonomer.
In the above-mentioned polymkeric substance, the mol ratio of said comonomer and said acrylic amide can be 0.3%-0.6%, specifically can be 0.3%-0.35%, 0.35%-0.4%, 0.4%-0.5% or 0.5%-0.6%.
In the above-mentioned polymkeric substance; When arm B is methacrylamide homopolymer; Said polymine can be 3800000g/mol-4200000g/mol for the weight-average molecular weight Mw of the star-like SEPIGEL 305 base polymer of nuclear; Number-average molecular weight Mn can be 1800000g/mol-2900000g/mol, and branching factor g can be 0.49-0.77.
In the above-mentioned polymkeric substance, when arm B was the multipolymer that is formed by acrylic amide and comonomer, said polymine can be 16dL/g-21dL/g for the intrinsic viscosity of the star-like SEPIGEL 305 base polymer of nuclear.
In the above-mentioned polymkeric substance, said comonomer is selected from SSS, 2-acrylamido-2-methyl propane sulfonic acid sodium and the octadecyl dimethyl allene ammonium chloride any.
Can confirm the branched structure of above-mentioned polymine in order to following method: adopt branching factor g to describe the degree of branching of star-like SEPIGEL 305 homopolymer (star-like PAM) for the star-like SEPIGEL 305 homopolymer of nuclear; It is defined as: when molecular weight is identical, and all square rotation radius R of branched polymer chain
G, LAll square rotation radius R with the linear macromolecule chain
G, SThe ratio.G＜1, and the g value reduces with number of branches purpose increase in the molecule.Provided all square rotation radius R of linear polypropylene acid amides homopolymer and star-like SEPIGEL 305 homopolymer among Fig. 3
gRelational expression with molecular weight Mw.Can know that by Fig. 3 along with the increase of polymine (PEI) molecular weight, the branching factor of corresponding star-like PAM reduces thereupon, simultaneous verification the branched structure of star-like PAM.
Above-mentioned polymine is the star-like SEPIGEL 305 base polymer of nuclear; When arm B was methacrylamide homopolymer, said polymine specifically can be 3800000-4200000g/mol, 3980000-4140000g/mol, 3800000g/mol, 3980000g/mol, 4080000g/mol, 4130000g/mol, 4140000g/mol or 4200000g/mol for the weight-average molecular weight Mw of the star-like SEPIGEL 305 base polymer of nuclear; Number-average molecular weight Mn specifically can be 1800000-2900000g/mol, 1800000-2310000g/mol, 1800000g/mol, 1840000g/mol, 1970000g/mol, 2310000g/mol, 2870000g/mol or 2900000g/mol; Branching factor g specifically can be 0.49-0.70,0.55-0.70,0.49,0.55 or 0.77.
Above-mentioned polymine is the star-like SEPIGEL 305 base polymer of nuclear, and when arm B was the multipolymer that is formed by acrylic amide and comonomer, its intrinsic viscosity specifically can be 16-17dL/g or 17-21dL/g.
Utilize polymine shown in the thioxanthone modified polyethyleneimine light trigger catalyzed polymerization formula provided by the invention (II) for the method for star-like SEPIGEL 305 base polymer of nuclear comprise the steps: under the illumination with the acrylamide triggered aqueous solution of thioxanthone modified polyethyleneimine shown in the said formula (I) or; The mixed aqueous solution polyreaction of acrylic amide and said comonomer obtains the star-like SEPIGEL 305 base polymer of polymine shown in the said formula (II) for nuclear; The mol ratio of said comonomer and acrylic amide is 0.3%-0.6%.
Among the above-mentioned preparation method, said comonomer can be selected from sodium p styrene sulfonate, 2-acrylamido-2-methyl propane sulfonic acid sodium and octadecyl dimethyl allene ammonium chloride.
Among the above-mentioned preparation method, the concentration of aqueous solution of thioxanthone modified polyethyleneimine can be 10-30 * 10 shown in the said formula (II)
-6Mol/L; The massfraction of the aqueous solution of said acrylic amide can be 25%-30%, and preferred 30%; The massfraction of said acrylic amide and the monomeric mixed aqueous solution of copolymerization can be 25%-30%, and preferred 30%.
Among the above-mentioned preparation method, said polyreaction is carried out in the silica glass groove.
Among the above-mentioned preparation method, the light source of said polyreaction is the high voltage mercury lamp of 100W-1000W, preferred 500W high voltage mercury lamp.
Among the above-mentioned preparation method, said silica glass groove is placed on the top of the said high voltage mercury lamp 10cm-15cm of distance.
Among the above-mentioned preparation method, the mol ratio of said comonomer and acrylic amide specifically can be 0.3%-0.35%, 0.35%-0.4%, 0.4%-0.5% or 0.5%-0.6%.
Among the above-mentioned preparation method, the temperature of said polyreaction can be 10 ℃-45 ℃, preferred 30 ℃; The time of said polyreaction can be 30min-70min, specifically can be 30min or 40min.
The end capped polymine light trigger of a kind of water-soluble thioxanthone provided by the invention; This initiator has dendritic structure; Has higher light-initiated performance, for having bigger realistic meaning through light-initiated aqueous solution polymerization prepared in reaction practicality three-dimensional polymer.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of TX-PEI600, TX-PEI800, TX-PEI3000 and TX-PEI10000.
Fig. 2 is the infrared spectrum of TX-PEI600, TX-PEI800, TX-PEI3000 and TX-PEI10000.
Fig. 3 is all square rotation radius R of linear polypropylene acid amides homopolymer and star-like SEPIGEL 305 homopolymer
gRelation curve with molecular weight Mw.M at known star-like PAM
wAfter, bring the R of LPAM into
gVs.M
wObtain the R of the LPAM under the corresponding molecular weight in the relational expression
g, through both R
gRatio can obtain the branching factor of this star-like PAM.
Fig. 4 is for PEI1800 being the GPC spectrogram of the PEI1800-PAM of nuclear.
Fig. 5 is the mensuration spectrogram of partly hydrolysed PEI1800-PAM intrinsic viscosity in 1mol/L NaCl.
Fig. 6 is the infrared spectrogram of partly hydrolysed PEI1800-PAM.
Fig. 7 is the nucleus magnetic hydrogen spectrum figure of partly hydrolysed PEI1800-PAM.
Fig. 8 is the mensuration spectrogram of PEI10000 for the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer intrinsic viscosity of nuclear.
Fig. 9 is the infrared spectrum of PEI10000 for the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear
Figure 10 is the nucleus magnetic hydrogen spectrum figure of PEI10000 for the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear.
Figure 11 is the viscosity-concentration relationship curve of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer.
Figure 12 is the viscosity-temperature dependency curve of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer.
Figure 13 is the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear and the flow performance curve after line style acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer shearing for PEI10000.
Figure 14 is the star-like partially hydrolyzed polyacrylamide of nuclear and the flow performance curve of linear partially hydrolyzed polyacrylamide for PEI10000.
Figure 15 is the flow performance curve after partly hydrolysed PEI600-PAM and partly hydrolysed PEI1800-PAM shear.
Figure 16 is the flow performance curve of different concns SHMPAM-0.3 after shearing.
Figure 17 is the oil displacement experiment result of PEI10000 for the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
The present invention adopts branching factor g to describe the degree of branching of star-like SEPIGEL 305 homopolymer (star-like PAM),
It is defined as: when molecular weight is identical, and all square rotation radius R of branched polymer chain
G, LAll square rotation radius R with the linear macromolecule chain
G, SThe ratio.
The preparation of thioxanthone modified polyethyleneimine shown in embodiment 1, the formula (I)
(1) preparation of 2-glycidoxy thioxanthone
The 16g thiosalicylic acid is dissolved in the 150mL vitriol oil stirring at room 10min; Slowly drip 44g phenol, react 1h under the room temperature, be warmed up to 80 ℃ of reaction 2h down then, hold over night.Reaction solution is slowly poured in the 1500mL boiling water, finished and continue to boil 30min; Be cooled to filter about 60 ℃, obtain intermediate product 2-hydroxyl thioxanthone after the oven dry.13.68g 2-hydroxyl thioxanthone, 21g Anhydrous potassium carbonate, 100mL epoxy chloropropane are joined in the 120mL toluene; 80 ℃ are reacted 12h down; React 12h down at 135 ℃ then; React the cooled and filtered that finishes, revolve and do excessive epoxy chloropropane and solvent, residue utilizes chloroform extraction to obtain 80.5g 2-glycidoxy thioxanthone.
(2) preparation of thioxanthone modified polyethyleneimine
1g2-glycidoxy thioxanthone is dissolved in the chloroform of 10mL that (dissolving is not exclusively down for low temperature; Can dissolve fully after the heating); Add the 0.4g polymine, its weight-average molecular weight Mw is respectively: 600g/mol (N=1), 1800g/mol (N=3); 3000g/mol (N=6) or 10000g/mol (N=16) (ratio of quality and the number of copies of 2-glycidoxy thioxanthone and the reaction of corresponding polymine is 5: 2) are warming up to 60 ℃ of reaction 24h down.After reaction finishes solution poured into the sedimentation and filtration drying obtains the thioxanthone modified polyethyleneimine in the 100mL sherwood oil; Be labeled as successively: thioxanthone end-blocking PEI600 (TX-PEI600); Thioxanthone end-blocking PEI1800 (TX-PEI1800), thioxanthone end-blocking PEI3000 (TX-PEI3000) and thioxanthone end-blocking PEI 10000 (TX-PEI0000).
The hydrogen nuclear magnetic resonance spectrogram of gained thioxanthone end-blocking PEI is as shown in Figure 1, and its spectral data is following: thioxanthone end-blocking PEI600 (TX-PEI600):
1H NMR (CDCl
3, 300MHz): δ 8.59-7.22 (phenyl ring), 4.14-4.00 (OCH
2), 3.67-2.67 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.49-0.82 (CH
2); Thioxanthone end-blocking PEI1800 (TX-PEI1800):
1H NMR (CDCl
3, 300MHz): δ 8.46-7.20 (phenyl ring), 4.13-3.86 (OCH
2), 3.68-2.67 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.26-0.82 (CH
2); Thioxanthone end-blocking PEI3000 (TX-PEI3000):
1H NMR (CDCl
3, 300MHz): δ 8.60-7.18 (phenyl ring), 4.33-3.85 (OCH
2), 3.70-2.65 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.52-0.81 (CH
2); Thioxanthone end-blocking PEI10000 (TX-PEI0000):
1H NMR (CDCl
3, 300MHz): δ 8.30-6.91 (phenyl ring), 4.76-3.90 (OCH
2), 3.73-2.66 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.49-0.82 (CH
2).
The infrared spectrum of gained thioxanthone end-blocking PEI is as shown in Figure 2, and its spectral data is following: thioxanthone end-blocking PEI600 (TX-PEI1600): FT-IR (KBr): 3353cm
-1(O-H, N-H), 2933cm
-1(C-H), 1632cm
-1(C=O); Thioxanthone end-blocking PEI1800 (TX-PEI1800): 3369cm
-1(O-H, N-H), 2936cm
-1(C-H), 1632cm
-1(C=O); Thioxanthone end-blocking PEI3000 (TX-PEI3000): 3362cm
-1(O-H, N-H), 2934cm
-1(C-H), 1632cm
-1(C=O); Thioxanthone end-blocking PEI10000 (TX-PEI0000): 3365cm
-1(O-H, N-H), 2935cm
-1(C-H), 1632cm
-1(C=O).
The results of elemental analyses of gained thioxanthone end-blocking PEI is seen table 1.
The ultimate analysis of the different thioxanthone end-blocking of table 1 PEI
The preparation of embodiment 2, star-like methacrylamide homopolymer
The preparation massfraction is 30% acrylamide solution 100mL (containing the 30g acrylic amide); Pour in the rectangle silica glass groove reaction solution into (150 * 90 * 40mm); Add thioxanthone modified polyethyleneimine (TX-PEI1800) 0.0027g, the concentration of thioxanthone modified polyethyleneimine (TX-PEI1800) is 15 * 10
-6Mol/L; Behind the letting nitrogen in and deoxidizing 30min glass guide channel sealing is placed on the top apart from 500W high voltage mercury lamp 15cm; This moment ultraviolet ray is through shining reaction solution behind the filter plate ZJB360,30 ℃ down reaction 30min obtain the block of star-like SEPIGEL 305 homopolymer, shred, obtain the star-like SEPIGEL 305 homopolymer (PEI1800-PAM) of thioxanthone modified polyethyleneimine after the absolute ethyl alcohol deposition, drying for nuclear; Reaction conversion ratio is 99.6%, and its GPC curve is as shown in Figure 4.
Its weight-average molecular weight Mw is: 4130000g/mol, number-average molecular weight Mn is: 184000g/mol, branching factor g are 0.70.
In kind obtain PEI600-PAM, PEI3000-PAM and PEI10000-PAM; Its weight-average molecular weight Mw is respectively: 3980000,414000 and 4080000g/mol; Number-average molecular weight Mn is respectively: 2310000,1970000 and 2870000g/mol, and branching factor g is respectively 0.77,0.55 and 0.49.
The preparation of embodiment 3, the star-like SEPIGEL 305 homopolymer of partly hydrolysed
The preparation massfraction is 25% acrylamide solution 100mL (containing the 25g acrylic amide); Pour in the rectangle silica glass groove reaction solution into (150 * 90 * 40mm); Add thioxanthone modified polyethyleneimine (TX-PEI1800) 0.0018g, the concentration of thioxanthone modified polyethyleneimine (TX-PEI1800) is 10 * 10
-6Mol/L; Behind the letting nitrogen in and deoxidizing 30min glass guide channel sealing is placed on the top apart from 500W high voltage mercury lamp 10cm; Ultraviolet ray this moment is reacted the block that 30min obtains star-like SEPIGEL 305 homopolymer through shining reaction solution behind the filter plate ZJB360 down at 30 ℃, shreds; Add 10wt%NaOH solution 70mL; After absolute ethyl alcohol deposition, drying behind 90 ℃ of hydrolysis 3h, obtain the partly hydrolysed star-like SEPIGEL 305 homopolymer of thioxanthone modified polyethyleneimine for nuclear, its mensuration spectrogram of intrinsic viscosity in 1mol/L NaCl is as shown in Figure 5, and ir spectra and nucleus magnetic hydrogen spectrum are respectively like Fig. 6 and shown in Figure 7.
Its intrinsic viscosity is 22.45dL/g, and viscosity-average molecular weight is 12390000g/mol.
In kind obtain partly hydrolysed PEI600-PAM, PEI3000-PAM and PEI10000-PAM; Its intrinsic viscosity is respectively: 19.82dL/g, 21.45dL/g, 20.12dL/g, viscosity-average molecular weight is respectively: 10600000g/mol, 11700000g/mol, 10800000g/mol.
The preparation of embodiment 4, star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer
The preparation massfraction is 30% solution 100mL; Solute is that acrylic amide and octadecyl dimethyl-allyl ammonium chloride (wherein contain 30g acrylic amide and 0.49g octadecyl dimethyl-allyl ammonium chloride; Wherein, The following document of synthetic reference of octadecyl dimethyl-allyl ammonium chloride: Xie Yu, Zhang Changhui, Xu Xuan. the synthetic and performance study of polymeric quaternary ammonium salts cats product. household chemicals science .2007.16-10); Wherein the mol ratio of octadecyl dimethyl-allyl ammonium chloride and acrylic amide is 0.35%; Reaction solution is poured in the rectangle silica glass groove (150 * 90 * 40mm), add 0.0036g thioxanthone modified polyethyleneimine (TX-PEI10000), the concentration of thioxanthone group is 25 * 10
-6Mol/L; Behind the letting nitrogen in and deoxidizing 30min glass guide channel sealing is placed on the top apart from 500W high voltage mercury lamp 15cm; This moment, ultraviolet ray was through shining reaction solution behind the filter plate ZJB360; React the block that 40min obtains star-like hydrophobically modified polyacrylamide down at 30 ℃, shred, add 10wt%NaOH solution 40-70mL; After absolute ethyl alcohol deposition, drying behind the 70-90 ℃ of hydrolysis 3h, obtain the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM-0.35) of thioxanthone modified polyethyleneimine for nuclear, the mensuration spectrogram of its intrinsic viscosity, infrared spectrum and nucleus magnetic hydrogen spectrum figure are respectively like Fig. 8, Fig. 9 and shown in Figure 10.
Its intrinsic viscosity is 17.24dL/g.
The mol ratio that in kind obtains octadecyl dimethyl-allyl ammonium chloride and acrylic amide is star-like acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer (being labeled as SHMPAM-0.3, SHMPAM-0.4, SHMPAM-0.5 and SHMPAM-0.6 respectively) of 0.3%, 0.4%, 0.5% and 0.6%, and its intrinsic viscosity is respectively: 20.40,17.10,16.97 and 16.06dL/g.
The anti-shear performance research of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of embodiment 5, embodiment 4
Join with SZ36-1 oil field, the Bohai Sea that to gather water be solvent, the practicality situation of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of investigating embodiment 4 is as going into.Join and gather that various ion content sees the following form 2 in the water:
Table 2 is joined the polywater particle and is formed (mg/L)
With PEI10000 is nuclear, during different hydrophobic monomer content, 45 ℃ down the dissolution time of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymers see table 3.
The solvability of the star-like acrylic amide of table 3 embodiment 4/octadecyl dimethyl-allyl ammonium chloride copolymer
With TX-PEI10000 is nuclear, and during different hydrophobic monomer content, the star-like hydrophobically modified acrylic amide of the embodiment 4/sticking dense curve of octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM) under 65 ℃ seen Figure 11.Wherein, The preparation method of line style acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer (LHMPAM-0.4) is following: the preparation massfraction is 30% solution 100mL; Solute is acrylic amide and octadecyl dimethyl-allyl ammonium chloride (wherein containing 30g acrylic amide and 0.56g octadecyl dimethyl-allyl ammonium chloride); Wherein the mol ratio of octadecyl dimethyl-allyl ammonium chloride and acrylic amide is 0.40%; Reaction solution is poured in the beaker of 250mL, added 0.009g water-soluble azo initiator V50, behind the letting nitrogen in and deoxidizing 30min beaker sealing is placed on the baking oven internal reaction 4h under 40 ℃; Obtain the block of line style hydrophobically modified polyacrylamide; Shred, add 10wt%NaOH solution 40-70mL, obtaining line style hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer (LHMPAM-0.40) after absolute ethyl alcohol deposition, the drying behind the 70-90 ℃ of hydrolysis 3h.
With TX-PEI10000 is nuclear, and during different hydrophobic monomer content, the star-like hydrophobically modified acrylic amide of the embodiment 4/viscosity-temperature curve of octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM) under 1750mg/L seen Figure 12.
With TX-PEI10000 is nuclear; During difference hydrophobic monomer content; 300mL copolymer solution (concentration is 1750mg/L) is poured in the glass jar of Waring whisking appliance of 1L, and next shelves of room temperature are sheared 20s, 65 ℃ measure solution shear down before and after viscosity change as shown in table 4.
The anti-shear performance of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of table 4 embodiment 4
The essential property of to sum up star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer shows: during identical octadecyl dimethyl-allyl ammonium chloride content, the AV of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride is higher than line style hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer; The content of octadecyl dimethyl-allyl ammonium chloride is 0.3% o'clock, and star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer just can satisfy notes and gather with the required basic demand of polymkeric substance.
The aging research of star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer of embodiment 6, embodiment 4
The use of the variation direct impact polymer of polymer solution viscosity under formation condition.Oxidative degradation and biological degradation possibly take place in polymkeric substance in the stratum.Prepare the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer solution (SHMPAM-0.3) of the PEI10000 of different concns for nuclear respectively, logical nitrogen 1h takes out sample test viscosity behind 65 ℃ of held different times, and the result sees table 5.
Can find out by table 5; PEI10000 has good permanent stability for the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer solution of nuclear, and when strength of solution was 1750mg/L, the sticking rate of the guarantor after 90 days was 81.3%; Viscosity is 72.8, meets index request basically.
Table 5PEI10000 is star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM-0.3) the solution long-term thermal stability of nuclear
The mobility control capability study of the star-type polymer of embodiment 7, embodiment 2-embodiment 4 preparations
1, experimental article and condition
The multi-functional physical chemistry drive apparatus of laboratory apparatus: HQY (Hai'an, Chinese Jiangsu); The displacement pump: the ISCO HPP, can carry out constant speed, constant voltage control, minimum flow rate 0.00001mL/min.
The circular homogeneous synthetic core of one dimension, wherein 1#-4# rock core cross-sectional area 10.75cm are used in experiment
2, length 29cm, the gas-phase permeation rate is about 3000mD, porosity about 30% (rock core water phase permeability and porosity are as the criterion with the experiment actual measurement), 5#-8# rock core cross-sectional area is 18.78cm
2, length 30.18cm, concrete rock core character is seen table 6 (LHPAM is linear partially hydrolyzed polyacrylamide in the table).Displacing velocity and requirement: initial water drive speed: 5m/d, polymer flooding and follow-up water drive speed 5m/d.
Experimental temperature: 65 ℃.
2, experimental result
The concrete outcome of experiment is seen Figure 13 to 16 and table 7 (LHPAM is linear partially hydrolyzed polyacrylamide in the table).Can know by table 7; When polymkeric substance does not contain hydrophobic monomer; The RF of star partly hydrolysed PEI1800-PAM and residual resistance factor are all than linear SEPIGEL 305 LPAM big (both molecular weight ratio are more approaching, and the solution AV is about 15mPas), and this possibly be because the molecular conformation of partly hydrolysed PEI1800-PAM more shrinks; Get into less capillary pore more easily; Therefore can get into more capillary pore, gather and cause core permeability decline bigger when driving, so RF is bigger.When changeing water drive more afterwards, owing in the more hole partly hydrolysed PEI1800-PAM is arranged all, the partly hydrolysed PEI1800-PAM that is trapped in the capillary pore is also more, so residual resistance factor also can be bigger.
When polymkeric substance contains hydrophobic monomer; PEI10000 obviously is better than LHMPAM (seeing Figure 13) for the injection efficiency of the star-like hydrophobically modified acrylic amide/octadecyl dimethyl-allyl ammonium chloride copolymer SHMPAM-0.3 of nuclear; Though the RF of SHMPAM-0.3 is lower than LHMPAM, the former residual resistance factor is but than the height of LHMPAM.This result possibly be because the conformation of SHMPAM-0.3 is shunk relatively equally; After when getting into hole, experiencing rock core shear fracture molecular interaction; SHMPAM-0.3 more is prone to get into porous medium, so injection efficiency is better relatively, can get into more hole simultaneously.The viscosity ratio LHMPAM of SHMPAM after getting in the porous medium is low, so RF is lower.During follow-up water drive, possibly be equally because to be trapped in the partly hydrolysed PEI1000-PAM of capillary pore more, so residual resistance factor big (seeing Figure 14).
During the difference degree of branching; The RF of polymkeric substance increases with the increase of the AV of solution; But the residual resistance factor of polymkeric substance increases (seeing table 7 and Figure 15) with the increase of polymeric degree of branching, possibly also be because the high polymkeric substance of the degree of branching more shrinks and can get into more hole.
Shown in figure 16, the working concentration that changes SHMPAM-0.3 can find that when polymer solution concentration is respectively 1200mg/L and 1500mg/L RF and residual resistance factor are respectively 15.3 (4.9) and 19.1 (6.4).
The essential property of table 6 rock core
RF and residual resistance factor after the different shearings of table 7
The displacement of reservoir oil performance study of the star-type polymer of embodiment 8, embodiment 4 preparations
1, experimental article and condition
The multi-functional physical chemistry drive apparatus of laboratory apparatus: HQY (Hai'an, Chinese Jiangsu); The displacement pump: the ISCO HPP, can carry out constant speed, constant voltage control, minimum flow rate 0.00001mL/min.
Two dimensional cross-section vertical heterogeneity synthetic core, cross-sectional area 19.86cm are used in experiment
2, length 29.17cm, each layer gas-phase permeation rate is respectively about 500mD, 1500mD and 4000mD from top to bottom, porosity about 30% (rock core water phase permeability and porosity are as the criterion with the experiment actual measurement).Concrete rock core character is seen table 8.
With comprehensive oil sample dehydration back, SZ36-1 oil field, the Bohai Sea and the composite simulated oil of kerosene, 65 ℃ of viscosity are 70mPas.
Output liquid is instantaneous during rock core metaideophone polymkeric substance moisturely requires 98%.
Displacing velocity and requirement: polymkeric substance and water drive speed: 3m/d.Polymers soln injects volume 0.3PV.
Experimental temperature: 65 ℃; Polymers soln: SHMPAM-0.3 is used in experiment, 1750mg/L, and sheared 20 seconds for one grade with Waring Blender 300mL solution preparation back.
Table 8 oil displacement experiment is with the essential property of rock core
2, experimental result
The result is shown in figure 17 for the SHMPAM-0.3 oil displacement experiment, and water drive is to 2.03PV, and the instantaneous water cut of extraction liquid is stable to be reached more than 98%, and injection pressure stabilizes to 0.030MPa, and the crude oil recovery percent of reserves is 30.98%; Metaideophone gathers 0.3PV afterwards, and injection pressure increases rapidly, the highest 0.15MPa that increases to, and the instantaneous water cut of extraction liquid descends, and minimumly drops to 80.5%, and the crude oil recovery percent of reserves rises simultaneously; After annotating the coalescence bundle, follow-up water drive begins, and injection pressure begins to descend, and the instantaneous water cut of extraction liquid slowly rises, and the different crude oils recovery percent of reserves is still rising, and after follow-up water drive finished, the crude oil recovery percent of reserves was 46.15%, compares with previous water drive and has improved 15.17%.
Claims (7)
1. thioxanthone modified polyethyleneimine, its structural formula are suc as formula (I):
Polymerization degree N=1-16 wherein.
2. thioxanthone modified polyethyleneimine according to claim 1 is characterized in that: said polymerization degree N is 1-6,3-6,1,3,6 or 16.
3. thioxanthone modified polyethyleneimine according to claim 1 and 2 is characterized in that: said thioxanthone modified polyethyleneimine prepares according to the method that comprises the steps: 2-glycidoxy thioxanthone and polymine react in solvent and promptly get product.
4. thioxanthone modified polyethyleneimine according to claim 3 is characterized in that: the polymerization degree of said polymine is 1-16, and weight-average molecular weight Mw is 600g/mol-10000g/mol; The ratio of quality and the number of copies of said 2-glycidoxy thioxanthone and said polymine is 5: 2.
5. according to claim 3 or 4 described thioxanthone modified polyethyleneimines, it is characterized in that: the polymerization degree of said polymine is 1-6,3-6,1,3,6 or 16.
6. according to arbitrary described thioxanthone modified polyethyleneimine among the claim 3-5, it is characterized in that: said solvent is chloroform, thionyl chloride, N, dinethylformamide or dithiocarbonic anhydride.
7. according to arbitrary described thioxanthone modified polyethyleneimine among the claim 3-6, it is characterized in that: the time of said reaction is 16 hours-36 hours; The temperature of said reaction is 40 ℃-70 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6025408A (en) * | 1997-03-27 | 2000-02-15 | First Chemical Corporation | Liquid thioxanthone photoinitiators |
| CN1472233A (en) * | 2003-06-05 | 2004-02-04 | 上海交通大学 | Water soluble high molecular thioanthrone light initiator and its preparation |
| CN1594369A (en) * | 2004-07-01 | 2005-03-16 | 上海交通大学 | Branch-shape macromolecular type thioxanthone photoinitiator and preparation method thereof |
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| CN101665575A (en) * | 2009-10-15 | 2010-03-10 | 上海交通大学 | Amphiphilic hyper-branched thioxanthone photoinitiator and preparation method thereof |
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| US6025408A (en) * | 1997-03-27 | 2000-02-15 | First Chemical Corporation | Liquid thioxanthone photoinitiators |
| CN1472233A (en) * | 2003-06-05 | 2004-02-04 | 上海交通大学 | Water soluble high molecular thioanthrone light initiator and its preparation |
| CN1594369A (en) * | 2004-07-01 | 2005-03-16 | 上海交通大学 | Branch-shape macromolecular type thioxanthone photoinitiator and preparation method thereof |
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| Title |
|---|
| 《Macromolecules》 20040925 Xuesong Jiang and Jie Yin "Dendritic Macrophotoinitiator Containing Thioxanthone and Coinitiator Amine" 7850-7853 1-7 第37卷, 第21期 * |
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