CN103159966A - Cross-linking formulations for forming quaternary ammonium salts - Google Patents
Cross-linking formulations for forming quaternary ammonium salts Download PDFInfo
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- CN103159966A CN103159966A CN2012100963556A CN201210096355A CN103159966A CN 103159966 A CN103159966 A CN 103159966A CN 2012100963556 A CN2012100963556 A CN 2012100963556A CN 201210096355 A CN201210096355 A CN 201210096355A CN 103159966 A CN103159966 A CN 103159966A
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- Prior art keywords
- quaternary ammonium
- cross
- ammonium salt
- solvent
- chemical formula
- Prior art date
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Links
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000009472 formulation Methods 0.000 title claims abstract description 27
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 24
- 238000004132 cross linking Methods 0.000 title description 24
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- -1 ether glycols Chemical class 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229960001701 chloroform Drugs 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims description 2
- 229960000655 ensulizole Drugs 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 239000004971 Cross linker Substances 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 125000001453 quaternary ammonium group Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000010612 desalination reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000036632 reaction speed Effects 0.000 description 7
- JTYUIAOHIYZBPB-UHFFFAOYSA-N 1-bromo-6-chlorohexane Chemical compound ClCCCCCCBr JTYUIAOHIYZBPB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
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- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- 125000001246 bromo group Chemical group Br* 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
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- 229920001451 polypropylene glycol Polymers 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- 229960003328 benzoyl peroxide Drugs 0.000 description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- FXLJHFCTYDFUER-UHFFFAOYSA-N 1-bromoprop-2-enylbenzene Chemical compound C=CC(Br)C1=CC=CC=C1 FXLJHFCTYDFUER-UHFFFAOYSA-N 0.000 description 1
- CIEWGZJDEDBECJ-UHFFFAOYSA-N 1-chloro-4-methylbenzene Chemical compound [CH2]C1=CC=C(Cl)C=C1 CIEWGZJDEDBECJ-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
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- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- MZNDIOURMFYZLE-UHFFFAOYSA-N butan-1-ol Chemical compound CCCCO.CCCCO MZNDIOURMFYZLE-UHFFFAOYSA-N 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- WNJYIHGQTOOFER-UHFFFAOYSA-L disodium;styrene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.C=CC1=CC=CC=C1 WNJYIHGQTOOFER-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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Abstract
The present invention provides a quaternary ammonium salt-forming cross-linked formulation comprising: a swellable polymer having an amino group; a crosslinker, wherein the crosslinker has at least two halogen substituents, and the halogen substituents are not the same; and a solution, wherein the solution includes a solvent dissolving the swellable polymer having the amino group.
Description
[technical field]
The present invention relates to a kind of cross-linked formulations, and particularly relate to a kind of cross-linked formulations that forms quaternary ammonium salt.
[prior art]
The various filtration material for desalinations that are applied to seawater, process water and waste water of each large factory active development of the world, filtration material for desalination is except wanting to process expeditiously in water salt, more wish to reduce working pressure, thereby reduce the clean water treatment cost because of low power consuming.
Have and study ionic polymer as filtration material for desalination; this material can under low pressure still have high-throughput; yet; in order to strengthen the physical strength of filtration material for desalination; usually can add linking agent and ionic polymer carries out crosslinked; yet the speed of the kind of linking agent and crosslinking reaction speed all can affect stability and the quality of filtration material for desalination.
In order further to improve the quality of filtration material for desalination, the present invention proposes a kind of cross-linked formulations, this cross-linked formulations comprises swellable polymer, linking agent and the solution with amino, and the resulting quaternary ammonium salt of crosslinking reaction that is undertaken by this cross-linked formulations can be used as filtration material for desalination.
[summary of the invention]
The invention provides a kind of cross-linked formulations that forms quaternary ammonium salt, comprising: with the swellable polymer of amino; Linking agent, wherein this linking agent has at least two halogenic substituents, and these halogenic substituents are not identical; And solution, wherein this solution comprises that dissolving is with the high molecular solvent of the swellable of amino.
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, and coordinate accompanying drawing, be described in detail below:
[description of drawings]
Figure 1A-1D is a series of Fourier transform infrared spectroscopy figure (FT-IR), in order to the crosslinking degree of the embodiment of the present invention to be described.
[embodiment]
The invention provides a kind of cross-linked formulations that forms quaternary ammonium salt, comprising: with the swellable polymer of amino; Linking agent, wherein linking agent has at least two halogenic substituents, and these halogenic substituents are not identical; And solution, wherein solution comprises that dissolving is with the high molecular solvent of the swellable of amino, protonic solvent (protic solvent), non-solvent or above-mentioned combination.So-called " swellable (water-swellable) polymer " means polymer itself and can expand by absorbing water herein, and this polymer can absorb large quantity of moisture and can not cause it to dissolve in water.
Above-mentioned swellable polymer with amino is formed with the monomer polymerization of chemical formula (I-3) by following chemical formula (I-1), chemical formula (I-2):
Above-mentioned linking agent is selected from many haloalkanes, phenyl polyhalide, many halogenated heterocyclics or many halos polymer, the compound of chemical formula (II), chemical formula (III) or chemical formula (IV) for example,
Wherein A is selected from C
1-C
25Alkylidene group (alkylene), C
6-C
25Arylidene (arylene) or C
7-C
25Inferior aralkyl (aralkylene); R
1, R
2Be selected from independently of one another Cl, Br or I, and R
1≠ R
2
R wherein
3, R
4, R
5Be selected from independently of one another replacement or unsubstituted aryl (aryl) or acryl series (acrylic) structure, as
R
6, R
9Be selected from independently of one another H or CH
3R
7, R
8Be selected from independently of one another CH
2Cl, CH
2Br, CH
2I； R
10, R
11Be selected from independently of one another H, CH
3, CH
2Cl, CH
2Br, CH
2I, wherein R
7≠ R
10, R
8≠ R
11, wherein a, b, c are the number of repeating unit, and a, b, c are 1～1000 integer independently of one another.
R wherein
12, R
13Be selected from independently of one another Cl, Br or I, and R
12≠ R
13, wherein d, e are the number of repeating unit, and d, e are 1～1000 integer independently of one another.
Linking agent and be 0.01-10 with the part by weight between the swellable polymer of amino, however the ratio of linking agent is not as limit, and those skilled in the art can adjust according to the demand of practical application.When the linking agent ratio is higher, can obtain the comparatively fine and close quaternary ammonium salt of structure, when the linking agent ratio is low, can obtain the comparatively loose quaternary ammonium salt of structure.
Should be noted, the quaternary ammonium salt that makes by cross-linked formulations of the present invention can further form fiber (fiber) by the spinning step, because the spinning time may need several hours, when so if rate of crosslinking is too fast, can cause viscosity (viscosity) to rise rapidly, make quaternary ammonium salt can't carry out the spinning step, therefore, the present invention is by the not identical speed of slowing down crosslinking reaction of those halogenic substituents in linking agent.
In addition, the quaternary ammonium salt that makes by cross-linked formulations of the present invention can further be formed on carrier layer by coating (coating) step, to be made into filtration material for desalination, yet, when if rate of crosslinking is too fast, can cause viscosity (viscosity) to rise rapidly, can make that the thickness of coating is too thick or thickness is wayward, therefore, the present invention is by the not identical speed that regulates and controls crosslinking reaction of those halogenic substituents in linking agent.
in one embodiment, use the identical different linking agent of polymer collocation, experimental result is found at ambient temperature, use 1-bromo-6 chlorohexane (1-bromo-6-chloro-hexane, BCH) rate of crosslinking is slower than 1, 6-dibromo-hexane (1, 6-dibromo hexane, DBH), this is because bromine atoms and chlorine atom are when carrying out crosslinking reaction, bromine atoms is easier and high molecular weight reactive Cheng Jian than chlorine atom, therefore, both sides are that the rate of crosslinking of the linking agent of bromine atoms can be faster than one side bromine linking agent of chlorine on one side, hence one can see that, the linking agent that uses both sides to have different halogens can slow down the speed of crosslinking reaction really, therefore, those skilled in the art can be according to the needs of actual procedure (spinning process or coating process), add dissimilar linking agent, speed with the regulation and control crosslinking reaction.
Above-mentioned dissolving is high polar solvent with the high molecular solvent of the swellable of amino, N for example, N-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl formamide (Dimethylformamide, DMF), methyl-sulphoxide (Dimethyl sulfoxide, DMSO), alcohols, N-Methyl pyrrolidone (N-methyl pyrrolidinone, NMP) etc.
Above-mentioned protonic solvent comprises water, acid or alcohols.Acids comprises formic acid (formic acid), acetic acid (acetic acid), citric acid (citric acid), succsinic acid (succinic acid), hydrochloric acid (hydrochloric acid) or above-mentioned combination.
Alcohols can be monohydroxy-alcohol or polyvalent alcohol, and monohydroxy-alcohol is methyl alcohol (methanol), ethanol (ethanol), n-propyl alcohol (n-propanol), Virahol (isopropanol), propyl carbinol (n-butanol) or Pentyl alcohol (n-pentanol) for example.
Polyvalent alcohol comprises glycols, many alcohols, ether glycols or above-mentioned combination.glycols is ethylene glycol for example, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexanediol, cyclohexyl dimethanol (Cyclohexyldimethanol, CHDM), ethohexadiol, neopentyl glycol (Neopentyl glycol, NPG), neopentyl glycol (Trimethylpentanediol, TMPD), xylyl alcohol, dihydroxy-benzene, cresorcin or dihydroxyphenyl propane (Bisphenol-A), poly adipate succinic acid ester [Poly (butanediol-co-adipate) glycol, PBA], polytetramethylene ether diol (Polytetramethylene glycol, PTMEG), polypropylene glycol (Polypropylene glycol, PPG), polyoxyethylene glycol (Polyethylene glycol, PEG).
Many alcohols comprise polyester polyol, polyether glycol, polycarbonate polyol, polycaprolactone polyol, polyacrylate polyol, for example glycerol, trimethylammonium alcohol propane (Trimethylolpropane), tetramethylolmethane (Pentaerythritol), benzenetriol.
The ether glycols for example comprises Diethylene Glycol, triethylene glycol, dipropylene glycol, tripropylene glycol.
above-mentioned non-solvent refers to and the immiscible solvent of swellable polymer with amino, because the swellable polymer with amino is ionic polymer, therefore non-solvent is low polar solvent, non-solvent comprises tetrahydrofuran (THF) (Tetrahydrofuran, THF), methylene dichloride (dichloromethane, DCM), trichloromethane (chloroform), straight or branched alkanes (pentane, hexane (hexane), heptane (heptane)), benzene (benzene), toluene (toluene) or acetone (acetone) etc.
Above-mentioned dissolving is with the high molecular solvent of the swellable of amino: the part by weight of protonic solvent or non-solvent is about 9/1-5/5.
In one embodiment, dissolving is N,N-dimethylacetamide (DMAc) with the high molecular solvent of the swellable of amino, and protonic solvent is ethanol (ethanol), and the mixed weight ratio of the former with the latter is 9: 1.
In another embodiment, dissolving is N,N-dimethylacetamide (DMAc) with the high molecular solvent of the swellable of amino, and non-solvent is tetrahydrofuran (THF) (Tetrahydrofuran, THF), and the mixed weight ratio of the former with the latter is 5: 5.
Should be noted protonic solvent and with forming hydrogen bond between the swellable polymer of amino, this hydrogen bond can slow down crosslinking reaction speed.In addition, because non-solvent can not dissolve each other with the swellable polymer, therefore, the existence of non-solvent can reduce the chance of linking agent and the collision of swellable polymer, and then reduces crosslinking reaction speed.Hence one can see that, and those skilled in the art can mix one or more protonic solvents or non-solvent according to the needs of actual procedure, to regulate and control required crosslinking reaction speed.
Moreover in one embodiment, cross-linked formulations provided by the present invention at room temperature (20-25 ℃) namely begins to carry out the part crosslinking reaction, can help by heating steps the carrying out of crosslinking reaction.In another embodiment, cross-linked formulations provided by the present invention needs just can carry out crosslinking reaction by heating steps.
In sum, cross-linked formulations provided by the present invention can be in order to regulate and control crosslinking reaction speed, (for example spinning forms fiber to be beneficial to follow-up ion Process Technology of Polymer process, or coat form coating layer on carrier layer), and the fiber of follow-up process gained or coating layer can pass through heating steps again, make polymer and linking agent fully crosslinked, the material of last gained can be used as filtration material for desalination.
[embodiment]
Embodiment 1 synthetic cross-linking agent chemical structure (III): Poly (styrene-co-vinylbenzylhalide) copolymer
Get respectively 2g/1g/1g vinylbenzene (Styrene)/1-chloro-4-methyl-benzene (vinylbenzylchloride)/brooethyl vinylbenzene (vinylbenzylbromide) (each monomer ratio is decided by demand), and add 20ml tetrahydrofuran (THF) (THF), react under nitrogen, temperature is risen to 70 ℃ again, then add initiator benzoyl peroxide (benzoperoxide, BPO) (BPO solution: 0.04g/5ml THF), reaction is 3 hours under 70 ℃ for solution.Again with product with the methyl alcohol sedimentation, filter and can obtain Poly (styrene-co-vinylbenzylhalide) copolymer after draining.
Embodiment 2 synthetic cross-linking agent chemical structures (IV): Halide-methylated Polysulfone (PSF-X)
3 gram polysulfones (polysulfone) (molecular weight 35,000) are mixed with 80ml chloroform (chloroform), be heated to 50 ℃ under nitrogen it is dissolved fully, to form mixing solutions.
With 2g formaldehyde (P-formaldehyde), 0.35g tin tetrachloride (SnCl
4), 4.3g trimethylchlorosilane (trimethylsilylchloride, SiMe
3Cl) with 5.9g bromotrimethylsilane (trimethylsilylbromide, SiMe
3Br) (SiMe
3Cl and SiMe
3The ratio of Br is looked the actual needs adjustment) jointly be dissolved in 30ml chloroform (chloroform), then mentioned solution is added in polysulfones solution be mixed together, with 50 ℃ of reflux 48 hours.Reaction adds methyl alcohol that product is precipitated after finishing, and can get at last white solid Halide-methylated Polysulfone (PSF-X).
The embodiment 3 swollen polymer Poly of synthesis of soluble (sodium styrene sulfate-co-4-vinylpyridine-co-styrene)
Get 230g Sodium styrene sulfonate (sodium styrene sulfate), 460g 4-vinylpyridine (4-vinylpyridine), 230g vinylbenzene (styrene) (each monomer ratio can be adjusted according to circumstances), 1150ml deionized water, 1150ml Virahol (IPA) stirring and dissolving, pass into nitrogen, under 70 ℃ of constant temperature, reaction is 30 minutes, to form mixing solutions.
Get 9.2g Potassium Persulphate (potassium persulfate, KPS) and be dissolved in the 230ml deionized water, more slowly splash in above-mentioned mixing solutions, react and namely completed in 3 hours.The macromolecular solution that has reacted can get Off-white solid Poly (sodium styrene sulfate-co-4-vinylpyridine-co-styrene) with the salt solution sedimentation after drying, washing purifying.
The synthetic quaternary ammonium salt of embodiment 4
The polymer of embodiment 3 is formulated in N, in N-N,N-DIMETHYLACETAMIDE (DMAc) solvent, solid content is 20wt%, linking agent 1-bromo-6 chlorohexanes (1-bromo-6-chloro-hexane, BCH) that proportionally add 0.3 times (0.3 equivalent) being equivalent to macromolecular chain pyridine (pyridine) molar content.
Get above-mentioned appropriate sample and carry out the viscosity monitoring on viscosity apparatus, viscosity measurement and temperature of reaction are all at room temperature carried out, and every set time record viscosity numerical value change, experimental result is as shown in table 1.
Table 1
Comparative example 1
Experimental procedure, material, measuring method and implementation condition are with embodiment 4, and linking agent changes 1,6-dibromo-hexane (1,6-dibromo hexane, DBH) into by BCH only, and the linking agent equivalents is still kept 0.3 equivalent.Experimental result is as shown in table 2.
Can be learnt by table 1 and the experimental result of table 2, than DBH, BCH viscosity under same experimental conditions rises slowly many.
Table 2
Embodiment 5 utilizes protonic solvent or non-solvent to control crosslinking reaction speed
The polymer of embodiment 3 is formulated in respectively in the solvent that is shown in table 3 (is respectively N, N-N,N-DIMETHYLACETAMIDE (DMAc), N, mixed solvent and the N of N-N,N-DIMETHYLACETAMIDE and tetrahydrofuran (THF) (THF), the mixed solvent of N-N,N-DIMETHYLACETAMIDE and alcohol), wherein the solution solid content is fixed on 23.5wt%.
Above-mentioned each batch solution is proportionally added respectively the 1-bromo-6 chlorohexane (1-bromo-6-chloro-hexane that are equivalent to macromolecular chain pyridine (pyridine) 0.3 equivalent, BCH) linking agent, get appropriate sample and carry out online viscosity monitoring on viscosity apparatus, Temperature Setting is at 25 ℃, change in time, every 0.5 hour record viscosity numerical value change, experimental result is as shown in table 3.
Data by table 3 can be learnt, add protonic solvent (as alcohol) or non-solvent (as tetrahydrofuran (THF)), really can slow down crosslinking reaction speed.
Table 3
Embodiment 6
The swellable molecule of embodiment 3 is mixed (75: 25,60: 40,50: 50 and 40: 60) by weight proportion with the polymer of embodiment 1 (linking agent), be formulated in respectively N, in the N-dimethylacetamide solvent, macromolecular solid content is 20wt%.
After mentioned solution is fully mixed, then with solution coat on glass baseplate, after 130 ℃ of crosslinked sclerosis, then confirm with FT-IR, experimental result as table 5 with as shown in Figure 1A-1D, by 1638cm
-1The FT-IR charateristic avsorption band can determine that mixing solutions has carried out crosslinking reaction.
Table 5
| Embodiment 3: the weight blending ratio of embodiment 1 | Accompanying drawing |
| 75∶25 | 1A |
| 60∶40 | 1B |
| 50∶50 | 1C |
| 40∶60 | 1D |
Embodiment 7
Implementation step is with embodiment 6, and difference is that macromolecular material changes swellable polymer and the embodiment 2 (linking agent) of embodiment 3 into, and blending ratio was respectively 70: 30,63: 37 and 37: 63, by 1638cm
-1The FT-IR charateristic avsorption band can determine that mixing solutions has carried out crosslinking reaction.
Although the present invention discloses as above with several preferred embodiments; yet it is not to limit the present invention; the technician who has common knowledge in technical field under any; without departing from the spirit and scope of the present invention; when can change arbitrarily and modify, so protection scope of the present invention is as the criterion when looking claims person of defining.
Claims (12)
1. cross-linked formulations that forms quaternary ammonium salt comprises:
Swellable polymer with amino;
Linking agent, wherein this linking agent has at least two halogenic substituents, and these halogenic substituents are not identical; And
Solution, wherein this solution comprises that dissolving is with the high molecular solvent of the swellable of amino.
2. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1 wherein should be formed with the monomer polymerization of chemical formula (I-3) by following chemical formula (I-1), chemical formula (I-2) with swellable polymer of amino:
R wherein
1Be selected from phenylbenzimidazole sulfonic acid base or alkyl group sulfonic group;
R wherein
2Be selected from
R wherein
3Be selected from
And the mol ratio of chemical formula (I-1), chemical formula (I-2) and chemical formula (I-3) is about 0.1-50: 1-99: 0.1-50.
3. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1, wherein this linking agent is selected from chemical formula (II), chemical formula (III) or chemical formula (IV),
Wherein A is selected from C
1-C
25Alkylidene group (alkylene), C
6-C
25Arylidene (arylene) or C
7-C
25Inferior aralkyl (aralkylene); R
1,
R2Be selected from independently of one another Cl, Br or I, and R
1≠ R
2
R wherein
3, R
4, R
5Be selected from independently of one another
R
6, R
9Be selected from independently of one another H or CH
3
R
7, R
8Be selected from independently of one another CH
2Cl, CH
2Br, CH
2I；
R
10, R
11Be selected from independently of one another H, CH
3, CH
2Cl, CH
2Br, CH
2I, wherein R
7≠ R
10, R
8≠ R
11, wherein a, b, c are the number of repeating unit, and a, b, c are 1～1000 integer independently of one another;
R wherein
12, R
13Be selected from independently of one another Cl, Br or I, and R
12≠ R
13, wherein d, e are the number of repeating unit, and d, e are 1～1000 integer independently of one another.
4. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1, wherein this solution also comprises protonic solvent or non-solvent.
5. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 4, wherein this dissolving is with the high molecular solvent of the swellable of amino: the part by weight of protonic solvent or non-solvent is about 9/1-5/5.
6. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 4, wherein this protonic solvent comprises water, acids or alcohols.
7. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 6, wherein this acids comprises formic acid, acetic acid, citric acid, succsinic acid, hydrochloric acid or above-mentioned combination.
8. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 6, wherein this alcohols comprises monohydroxy-alcohol or polyvalent alcohol.
9. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 8, wherein this monohydroxy-alcohol comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol or above-mentioned combination.
10. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 8, wherein this polyvalent alcohol comprises glycols, many alcohols, ether glycols or above-mentioned combination.
11. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 4, wherein this non-solvent comprises tetrahydrofuran (THF), methylene dichloride, trichloromethane, straight or branched alkanes, benzene, toluene, acetone or above-mentioned combination.
12. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1, wherein this linking agent account for the high molecular part by weight of this swellable with amino be 0.01-10 doubly.
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| CN1506035A (en) * | 2002-12-13 | 2004-06-23 | 莱雅公司 | Hair conditioning composition containing film forming gradient copolymer, airsol composition containing the same hair care composition and treatment method |
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| WO2011033261A1 (en) * | 2009-09-17 | 2011-03-24 | Unilever Plc | Use of branched addition copolymers in films and membranes |
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