阅读说明：本技术 聚合物珠及其应用 (Polymeric beads and its application ) 是由 马修·罗伊·雷蒙德 于 2018-02-07 设计创作，主要内容包括：本发明涉及用于生产聚合物珠的工艺,所述聚合物珠具有多孔聚合物基质,在所述多孔聚合物基质中分布有固体颗粒材料；所述工艺包括：(i)提供具有分散相和连续相的分散体,所述分散相包含：(a)可聚合单体组合物,(b)固体颗粒材料,(c)非聚合物致孔剂；以及(d)没有聚合物致孔剂；其中所述可聚合单体组合物包含：(e)至少一种单烯属不饱和单体,和(f)至少一种交联单体,所述至少一种交联单体具有被至少4个连续的非环原子隔开的至少两个烯属不饱和基团；以及(ii)在所述非聚合物致孔剂和固体颗粒材料的存在下使所述可聚合单体组合物聚合,以形成所述珠的所述多孔聚合物基质。(The present invention relates to the technique for producing polymeric beads, the polymeric beads have porous polymer matrix, and solid particulate materials are distributed in the porous polymer matrix；The technique includes: that (i) provides the dispersion with dispersed phase and continuous phase, and the dispersed phase includes: (a) polymerizable monomer composition, (b) solid particulate materials, (c) non-polymer pore-foaming agent；And there is no polymer pore-foaming agent (d)；Wherein the polymerizable monomer composition includes: (e) at least one single ethylenically unsaturated monomer, (f) at least one cross-linking monomer, at least one cross-linking monomer have by least four at least two ethylenically unsaturated groups that continuously non-annular atom separates；And (ii) polymerize the polymerizable monomer composition in the presence of non-polymer pore-foaming agent and solid particulate materials, to form the porous polymer matrix of the pearl.)

1. a kind of for producing the technique of polymeric beads, the polymeric beads have porous polymer matrix, described porous poly- Solid particulate materials are distributed in polymer matrix；The technique includes:

(i) dispersion with dispersed phase and continuous phase is provided, the dispersed phase includes:

(a) polymerizable monomer composition,

(b) solid particulate materials,

(c) non-polymer pore-foaming agent；And

(d) there is no polymer pore-foaming agent；

Wherein the polymerizable monomer composition includes:

(e) at least one single ethylenically unsaturated monomer, and

(f) at least one cross-linking monomer, at least one cross-linking monomer have that continuously non-annular atom separates by least four At least two ethylenically unsaturated groups；And

(ii) it polymerize the polymerizable monomer composition, To form the porous polymer matrix of the pearl.

2. technique according to claim 1, wherein at least one cross-linking monomer is selected from ethyleneglycol dimethacrylate Ester, poly(ethylene glycol) dimethylacrylate, methylene-bisacrylamide, triethylene glycol diacrylate, triethylene glycol diformazan Base acrylate, glycol diacrylate, diethylene glycol diacrylate, dimethacrylate, glycerol two Acrylate, glycerine dimethacrylate, 1,3 butyleneglycol diacrylate and 1,3 butylene glycol dimethylacrylate, 1, 3-propanediol diacrylate, 1,3- dimethacrylate, 1,3- Diacrylate, 1,3- pentanediol two Methacrylate, 1,4 butanediol diacrylate, 1,4- butanediol dimethylacrylate, two propylene of hexamethylene glycol Acid esters, hexamethylene glycol dimethylacrylate, decamethylene omega-diol diacrylate, decamethylene glycol dimethyl allene Acid esters, 2,2- dihydroxy methylpropane diacrylate, 2,2- dihydroxy methylpropane dimethylacrylate, two propylene of tripropylene glycol Acid esters, tripropylene glycol dimethylacrylate, (p-hydroxybenzene) propane of 2,2- bis- diacrylate, bis- (para hydroxybenzene of 2,2- Base) propane dimethylacrylate, 2,2,4- trimethyl -1,3- Diacrylate, 2,2,4- trimethyl -1,3- penta 2 Alcohol dimethylacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethylacrylate, and combinations thereof.

3. technique according to claim 1, wherein at least one cross-linking monomer is selected from trimethylolpropane tris propylene It is acid esters, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, sweet Oily triacrylate, glycerol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethylacrylate, three (2- hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, three hydroxyl of ethoxylation Trimethacrylate, propoxylation trimethylolpropane trimethacrylate, propoxylation trimethylolpropane tris Methacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethyl acrylic ester, propoxylated glycerol three Acrylate, propoxylated glycerol trimethyl acrylic ester, ethoxylation pentaerythritol triacrylate, ethoxylation Ji Wusi Alcohol trimethyl acrylic ester, pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate trimethyl acrylic ester, second Oxygroup pentaerythritol tetraacrylate, ethoxylation pentaerythritol tetramethylacrylate, pentaerythritol propoxylate 4 third Olefin(e) acid ester, pentaerythritol propoxylate tetramethyl acrylate, and combinations thereof.

4. technique according to any one of claim 1 to 3, wherein the solid particulate materials are magnetic.

5. technique according to claim 4, wherein the magnetic retention granular materials is selected from maghemite, magnetic iron ore, two Chromium oxide, and combinations thereof.

6. technique according to any one of claim 1 to 5, wherein the non-polymer pore-foaming agent is selected from toluene, benzene, fourth Alcohol, isooctanol, cyclohexanol, lauryl alcohol, isoamyl alcohol, tert-pentyl alcohol, methyl isobutyl carbinol, ethyl acetate, butyl acetate, positive heptan Alkane, isooctane, dichloroethanes, trichloro ethylene, dioctyl phthalate, dibutyl adipate and combinations thereof.

7. technique according to any one of claim 1 to 6, wherein the polymerizable monomer composition is comprising one kind or more A variety of functional monomers, the one or more functional monomer are provided with offer or after the reaction with ion exchange site The functional group of the polymer substrate of pearl.

8. technique according to claim 7, wherein the ion exchange site is the shape with amine functional group or acid functional group Formula.

9. polymeric beads, the polymeric beads include porous polymer matrix, and the porous polymer matrix, which has, is distributed in it In solid particulate materials, the polymer substrate (i) includes polymerized monomer residue below: (a) at least one monoene belongs to not It is saturated at least one cross-linking monomer of monomer and (b), at least one cross-linking monomer has by the continuous non-annular atom of at least four At least two ethylenically unsaturated groups separated, wherein the polymer substrate includes non-polymer pore-foaming agent and do not include poly- Close object pore-foaming agent.

10. polymeric beads, the polymeric beads include porous polymer matrix, and the porous polymer matrix, which has, is distributed in it In solid particulate materials, the polymer substrate (i) includes polymerized monomer residue below: (a) at least one monoene belongs to not It is saturated at least one cross-linking monomer of monomer and (b), at least one cross-linking monomer has by the continuous non-annular atom of at least four At least two ethylenically unsaturated groups separated, wherein the polymer substrate does not include pore-foaming agent.

11. polymeric beads according to claim 9, wherein the non-polymer pore-foaming agent is selected from toluene, benzene, butanol, different It is octanol, cyclohexanol, lauryl alcohol, isoamyl alcohol, tert-pentyl alcohol, methyl isobutyl carbinol, ethyl acetate, butyl acetate, normal heptane, different pungent Alkane, dichloroethanes, trichloro ethylene, dioctyl phthalate, dibutyl adipate and combinations thereof.

12. the polymeric beads according to any one of claim 9 to 11, wherein at least one cross-linking monomer is selected from second Diol dimethacrylate, poly(ethylene glycol) dimethylacrylate, methylene-bisacrylamide, triethylene glycol diacrylate Ester, triethylene glycol dimethacrylate, glycol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethyl Acrylate, glycerol diacrylate, glycerine dimethacrylate, 1,3 butyleneglycol diacrylate and 1,3 butylene glycol two Methacrylate, 1,3- propylene glycol diacrylate, 1,3- dimethacrylate, 1,3- pentanediol diacrylate Ester, 1,3- dimethacrylate, 1,4 butanediol diacrylate, 1,4- butanediol dimethylacrylate, six Methylene glycol diacrylate, hexamethylene glycol dimethylacrylate, decamethylene omega-diol diacrylate, ten methylenes Base diol dimethacrylate, 2,2- dihydroxy methylpropane diacrylate, 2,2- dihydroxy methylpropane dimethacrylate Ester, tripropylene glycol diacrylate, tripropylene glycol dimethylacrylate, 2,2- bis- (p-hydroxybenzene) propane diacrylate Ester, (p-hydroxybenzene) propane of 2,2- bis- dimethylacrylate, 2,2,4- trimethyl -1,3- Diacrylate, 2, 2,4- trimethyl -1,3- dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate Ester, and combinations thereof.

13. the polymeric beads according to any one of claim 9 to 11, wherein at least one cross-linking monomer is selected from three Hydroxymethyl-propane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythrite three Methacrylate, glycerol tri-acrylate, glycerol trimethacrylate, pentaerythritol tetraacrylate, pentaerythrite four Methacrylate, three (2- hydroxyethyl) isocyanurate triacrylates, three acrylic acid of ethoxylated trimethylolpropane Ester, ethoxylated trimethylolpropane trimethyl acrylic ester, propoxylation trimethylolpropane trimethacrylate, propoxylation Trimethylol-propane trimethacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethyl acrylic ester, Propoxylated glycerol triacrylate, propoxylated glycerol trimethyl acrylic ester, ethoxylation pentaerythritol triacrylate, Ethoxylation pentaerythritol acrylate trimethyl, pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate three Methacrylate, ethoxylation pentaerythritol tetraacrylate, ethoxylation pentaerythritol tetramethylacrylate, propoxyl group Change pentaerythritol tetraacrylate, pentaerythritol propoxylate tetramethyl acrylate, and combinations thereof.

14. the polymeric beads according to any one of claim 9 to 13, wherein the solid particulate materials are magnetic.

15. polymeric beads according to claim 14, wherein the magnetic retention granular materials is selected from maghemite, magnet Mine, chromium dioxide, and combinations thereof.

16. polymeric beads according to any one of claims 9 to 15, wherein polymer substrate functional group's function Change, the functional group provides ion-exchange capacity for the polymeric beads.

17. polymeric beads according to claim 16, wherein the ion-exchange capacity is by amine functional group or acid functional group It provides.

18. it is a kind of handle aqueous solution method, the method includes make the aqueous solution with according to any in claim 9 to 17 The polymeric beads contact of item.

19. a kind of method for removing dissolved organic carbon from aqueous solution makes the aqueous solution the method includes (i) and according to power Benefit requires any one of 9 to 17 polymeric beads to contact, and (ii) is removed to have from the aqueous solution and be adsorbed on it The polymeric beads of dissolved organic carbon.

20. a kind of method for removing ion from aqueous solution makes the aqueous solution the method includes (i) and according to claim 16 or 17 polymeric beads contact, and (ii) are removed from the solution and be experienced ion exchange with ion to be removed Polymeric beads.

Invention field

Present invention relates in general to polymeric beads, its preparation process and its applications.Polymeric beads are particularly suitable for from water It is middle to remove unacceptable pollutant, and it will be convenient that the present invention is therefore described herein with reference to the application.However, answering Work as understanding, polymeric beads can be also used for other application.

Background of invention

Most area in the world, the mankind cannot obtain enough drinking water.Therefore, important research has concentrated on It develops for removing the product and technique that pollutant is drunk to make it fit from water.

For example, polymeric beads (polymer bead) are applied to handle the water of dissolved organic carbon (DOC) pollution. In this case, the DOC in water can be adsorbed on the surface of polymeric beads.Polymeric beads may be provided with ion friendship Transducing power, to provide the product for being commonly known as ion exchange resin in this field.Ion-exchange capacity is provided for polymeric beads The pollutant that they can be improved removes efficiency.

In use, the polymeric beads with or without ion-exchange capacity can be filled into column, and be polluted Water purified by column.However, it is this from water remove pollutant " packed column " method may be in its efficiency by Limit.

Selectable method using the polymeric beads with or without ion-exchange capacity include by polymeric beads with Contaminant water stirs in tank.This method allows polymeric beads to have maximum contact with contaminant water.However, polymeric beads are (logical Normal very little) then it can be proved to be problematic from the separation in water.

Pollutant is removed from water in order to improve, polymeric beads can be provided with porosity, and which increase they and dirt Contaminate the surface area of water contact.

Be distributed in solid particulate materials therein polymeric beads can by increase polymeric beads density and/or Another property of polymeric beads, such as magnetic susceptibility can be used to be separated from the water by offer, to improve them from water Isolated easy degree.

WO 96/07675 discloses the polymeric beads for being incorporated to solid particulate materials.Polymeric beads can be provided with ion Exchange capacity, and be found effectively to remove pollutant from water, such as DOC.

Despite the presence of effective polymeric beads suitable for the removal pollutant from water, but still have an opportunity to develop new polymerization Object pearl technology, polymeric beads technology known to the technological improvement or at least provides the useful alternative of known polymeric beads technology Case.

Summary of the invention

The present invention provides the technique for producing polymeric beads, the polymeric beads have porous polymer matrix, In Solid particulate materials are distributed in the porous polymer matrix；The technique includes:

(i) dispersion with dispersed phase and continuous phase is provided, the dispersed phase includes:

(a) polymerizable monomer composition,

(b) solid particulate materials,

(c) non-polymer pore-foaming agent (non-polymeric porogen)；And

(d) there is no polymer pore-foaming agent；

Wherein the polymerizable monomer composition includes:

(e) at least one single ethylenically unsaturated monomer, and

(f) at least one cross-linking monomer, at least one cross-linking monomer have by least four continuously non-annular atom every At least two ethylenically unsaturated groups opened；And

(ii) make the polymerizable monomer composition in the presence of non-polymer pore-foaming agent and solid particulate materials Polymerization, to form the porous polymer matrix of the pearl.

Surprisingly, it has now been found that polymeric beads produced by the invention are relative to other known comparable Polymeric beads show it is superior from water remove pollutant ability.Without wishing to be bound by theory, it is believed that, make With the combination of specified cross-linking monomer Yu non-polymer pore-foaming agent and there is no polymer pore-foaming agent, is the polymer of polymeric beads Matrix provides specific form, this surprisingly enhances pollutant such as DOC from the removal in water.This form also by Think surprisingly to assign the pearl being thusly-formed improved engineering properties.

In one embodiment, the polymeric beads being thusly-formed are made to be subjected to cleaning, with from the polymerization of polymeric beads Non-polymer pore-foaming agent is removed in object matrix.

The present invention also provides polymeric beads, the polymeric beads include porous polymer matrix, the porous polymer Matrix, which has, is distributed in solid particulate materials therein, and the polymer substrate (i) includes polymerized monomer residue below: (a) At least one list ethylenically unsaturated monomer and (b) at least one cross-linking monomer, at least one cross-linking monomer have by least 4 At least two ethylenically unsaturated groups that a continuous non-annular atom separates, wherein the polymer substrate is caused comprising non-polymer Hole agent and do not include polymer pore-foaming agent.

Invention additionally provides polymeric beads, the polymeric beads include porous polymer matrix, the porous polymeric Object matrix, which has, is distributed in solid particulate materials therein, and the polymer substrate (i) includes polymerized monomer residue below: (a) at least one single ethylenically unsaturated monomer and (b) at least one cross-linking monomer, at least one cross-linking monomer have by extremely At least two ethylenically unsaturated groups that few 4 continuous non-annular atoms separate, wherein the polymer substrate does not include pore Agent.

Those skilled in the art will be familiar with pore-foaming agent and prepare the purposes in polymeric beads, in the poly- of entire polymeric beads Porosity is assigned in polymer matrix.Unexpectedly, non-polymer pore-foaming agent and specified cross-linking monomer according to the present invention It is applied in combination and produces the form of polymeric beads, which advantageously shows (i) and remove changing for pollutant such as DOC from water Into ability, and (ii) improved engineering properties.

In one embodiment, dispersed phase is organic phase and continuous phase is water phase.The organic phase of dispersion includes solid Granular materials.

In another embodiment, polymeric beads are provided with ion-exchange capacity.In this case, use can gather It closes monomer composition and produces polymeric beads, the polymerizable monomer composition includes one or more of functional monomers (functional monomer), the one or more functional monomer is with offer or providing after the reaction, there is ion to hand over The functional group of the polymer substrate of the pearl of exchange point.

In one embodiment, at least one single ethylenically unsaturated monomer and/or at least one cross-linking monomer are that have Offer or the after the reaction functional monomer of the functional group of offer ion exchange site.

In another embodiment, polymeric beads have ion-exchange capacity or provide ion exchange after experience reaction Ability.

In a further embodiment, polymer substrate includes the polymerized monomer residue of one or more of functional monomers, The functional monomer has the functional group for the ion exchange site for providing or providing polymeric beads after the reaction.

In another embodiment, at least one single ethylenically unsaturated monomer and/or at least one cross-linking monomer Polymerized monomer residue is functional monomer's residue of polymerization.

The present invention also provides the methods of processing aqueous solution, and this method includes making the aqueous solution and polymer of the invention Pearl or polymeric beads prepared in accordance with the present invention contact.The processing of aqueous solution may include pollutant is removed from solution, such as DOC。

Invention additionally provides the method for separating ion from aqueous solution, this method includes handing over solution with having ion The polymeric beads of the invention of transducing power or polymeric beads prepared in accordance with the present invention contact.

Other aspect and/or embodiment of the invention is described in more detail below.

Brief description

The present invention will be described with reference to non-limitative drawings below herein.

Fig. 1 is the SEM image for showing the smooth configuration of surface of appropriateness of polymeric beads according to the present invention；

Fig. 2 is shown using polymer pore-foaming agent and trimethylol-propane trimethacrylate (i.e. TMPTMA crosslinking list Body) preparation polymeric beads dimpled configuration of surface (pitted surface morphology) SEM image；

Fig. 3 be show using non-polymer pore-foaming agent and divinylbenzene (i.e. cross-linking monomer) preparation polymeric beads it is non- The SEM image of the sliding configuration of surface of ordinary light；

Fig. 4 illustrates use in Fig. 1 (new resin-is according to the present invention), Fig. 2 (PP resin-compare) and Fig. 3 (old resin- Compare) shown in type polymeric beads from three kinds of different water sample A, B and C derived from the U.S. DOC remove performance.

Fig. 5 is illustrated using the type shown in Fig. 1 (new resin-is according to the present invention) and Fig. 3 (old resin-compares) Polymeric beads remove performance from the DOC in the water sample derived from Australia.

Detailed description of the invention

Polymeric beads according to the present invention have porous polymer matrix.By having " porous " polymer substrate, it is intended that The polymer substrate for forming pearl structure has internal void (internal pore) and surface pore (gap (void)).

Polymeric beads according to the present invention have porous polymer matrix, and solid is distributed in the porous polymer matrix Granular materials.By in porous polymer matrix " distribution " have solid particulate materials, it is intended that solid particulate materials are comprised in (hole for being not exclusively located in polymer substrate is empty in polymer substrate itself and being dispersed in entire polymer substrate itself In).

As follows to will be discussed in more detail, the polymer substrate of polymeric beads formed by polymerizable monomer composition, and It and therefore include a part of polymerized monomer residue as its molecular structure from the composition.

Process according to the invention includes providing the dispersion with dispersed phase and continuous phase.Dispersion can be according to ability In domain prepared by well known technology.For example, dispersion can be suitable for carrying out the technology of well known dispersin polymerization or suspension polymerisation Mode prepare.

It will be understood by those skilled in the art that the dispersion phase coalescence of dispersion in order to prevent, can be desirable using stabilizer 's.The type of stabilizer used will depend on the property of dispersed phase and continuous phase.It can be used for preventing the suitable of dispersion phase coalescence Stabilizer include but is not limited to polyvinyl alcohol, gelatin, methylcellulose, Sodium Polyacrylate, or combinations thereof.

Based on the weight of entire dispersion, stabilizer is typically used with the amount of about 0.01wt% to about 5wt%, such as From about 0.05wt% to about 2.0wt%.

In one embodiment, dispersed phase is organic phase and continuous phase is water phase.In this case, the technique packet It includes and the dispersion of the organic phase and continuous water phase with dispersion is provided.

Dispersed phase includes polymerizable monomer composition.Polymerizable monomer composition itself includes at least one monoene category insatiable hunger And monomer.

Pass through " single ethylenically unsaturated monomer ", it is intended that having can polymerize to form the monomer of polymer double bond. Suitable monomer is the monomer that those can be polymerize by free radical process.Monomer should also be able to polymerize with other monomers. Determine that the factor of the combined polymerization (copolymerisability) of various monomers is documented in the art.For example, ginseng See: Greenlee, R.Z., in Polymer Handbook the 3rd edition (Brandup, J., and Immergut.E.H. are edited) Wiley:New York, 1989 Section II/53 page.Such monomer includes the monomer with logical formula (I):

Wherein U and W are independently selected from-CO₂H、-CO₂R¹、-COR¹、-CSR¹、-CSOR¹、-COSR¹、-CONH₂、- CONHR¹、-CONR¹ ₂, hydrogen, halogen and the C being optionally substituted₁-C₄Alkyl or U and W are formed together itself can be optional The substituted lactone in ground, acid anhydrides or imide ring (imide ring), wherein optional substituent group independently selected from hydroxyl ,- CO₂H、-CO₂R¹、-COR¹、-CSR¹、-CSOR¹、-COSR¹、-CN、-CONH₂、-CONHR¹、-CONR¹ ₂、-OR¹、-SR¹、- O₂CR¹、-SCOR¹And-OCSR¹；

V is selected from hydrogen, R¹、-CO₂H、-CO₂R¹、-COR¹、-CSR¹、-CSOR¹、-COSR¹、-CONH₂、-CONHR¹、- CONR¹ ₂、-OR¹、-SR¹、-O₂CR¹、-SCOR¹With-OCSR¹；

The wherein R¹Or each R¹Independently selected from the alkyl being optionally substituted, the alkenyl being optionally substituted, optionally The substituted alkynyl in ground, the aryl being optionally substituted, the heteroaryl being optionally substituted, the carbocylic radical being optionally substituted, The heterocycle that is optionally substituted, the aryl alkyl being optionally substituted, the heteroaryl alkyl being optionally substituted, optionally by It substituted alkylaryl, the alkyl heterocyclic being optionally substituted, the miscellaneous alkyl aryl being optionally substituted and is optionally taken The polymer chain in generation.

The R¹Or each R¹It can also be independently selected from the C being optionally substituted₁-C₂₂Alkyl is optionally substituted C₂-C₂₂Alkenyl, the C being optionally substituted₂-C₂₂Alkynyl, the C being optionally substituted₆-C₁₈Aryl, the C being optionally substituted₃-C₁₈ Heteroaryl, the C being optionally substituted₃-C₁₈Carbocylic radical, the C being optionally substituted₂-C₁₈Heterocycle, the C being optionally substituted₇- C₂₄Aryl alkyl, the C being optionally substituted₄-C₁₈Heteroaryl alkyl, the C being optionally substituted₇-C₂₄Alkylaryl, optionally by Substituted C₁-C₁₂Alkyl heterocyclic, the C being optionally substituted₄-C₁₈Miscellaneous alkyl aryl and the polymer chain being optionally substituted. Exemplary polymer chain includes selected from those of polyalkylene oxide, poly (arylene ether) and polyalkylene ether.

In one embodiment, R¹It can be independently selected from the C being optionally substituted₁-C₆Alkyl.

The example of single ethylenically unsaturated monomer includes but is not limited to maleic anhydride, N- alkyl maleimide, N- aryl horse Come acid imide, dialkyl fumarate and cyclic polymerization and closes monomer, acrylate and methacrylate, acrylic acid and metering system Acid, styrene, acrylamide, Methacrylamide and methacrylonitrile, the mixture of these monomers and these monomers and its The mixture of his monomer.

Other examples of useful single ethylenically unsaturated monomer include the following:

Methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), methacrylic acid fourth Ester (all isomers), 2-Ethylhexyl Methacrylate, isobornyl methacrylate, methacrylic acid, methacrylic acid Benzyl ester, phenyl methacrylate, methacrylonitrile, α-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-EHA, isobornyl acrylate, acrylic acid, third Olefin(e) acid benzyl ester, phenyl acrylate, acrylonitrile, styrene, function methacrylate, acrylate and styrene are selected from first Base glycidyl acrylate, 2-Hydroxyethyl methacrylate, hydroxy propyl methacrylate (all isomers), methacrylic acid Hydroxy butyl ester (all isomers), methacrylic N, N-dimethylamino ethyl ester, methacrylic acid N, N- diethylamino ethyl ester, Methacrylic acid triglycol ester, itaconic anhydride, itaconic acid, glycidyl acrylate, acrylic acid 2- hydroxyl ethyl ester, acrylic acid hydroxyl Propyl ester (all isomers), hy-droxybutyl (all isomers), acrylic acid N, N- dimethylamino ethyl ester, acrylic acid N, N- Diethylamino ethyl ester, acrylic acid triglycol ester, Methacrylamide, N methacrylamide, N, N- dimethyl allene acyl Amine, N- t-butylmethacrylamide, N- N-butyl methacrylamide, N- methylol methacrylamide, N- ethoxy first Base acrylamide, N tert butyl acrylamide, N- n-butyl acryloyloxy ethyl amide, N hydroxymethyl acrylamide, N- hydroxylethyl acyl Amine, vinyl benzoic acid (all isomers), diethylamino styrene (all isomers), Alpha-Methyl vinyl benzoic acid (all isomers), diethylamino α-methylstyrene (all isomers), to vinylbenzenesulfonic acid, to vinylbenzenesulfonic acid Sodium salt, methacrylic acid trimethoxysilyl propyl ester, methacrylic acid triethoxysilyl propyl ester, methacrylic acid Three butoxy silicyl propyl ester, dimethylaminoethyl acrylate methyl oxygen butylmethylsilyl propyl ester, methacrylic acid diethoxy first Base silicyl propyl ester, methacrylic acid Dibutoxymethyl silicyl propyl ester, methacrylic acid diisopropoxy methyl first Silylation propyl ester, dimethylaminoethyl acrylate methyl oxygroup silicyl propyl ester, methacrylic acid diethoxy silicyl propyl ester, methyl Acrylic acid dibutoxy silicyl propyl ester, methacrylic acid diisopropoxy silicyl propyl ester, acrylic acid trimethoxy first Silylation propyl ester, acrylic acid triethoxysilyl propyl ester, three butoxy silicyl propyl ester of acrylic acid, acrylic acid dimethoxy Butylmethylsilyl propyl ester, acrylic acid diethoxymethyl silicyl propyl ester, acrylic acid Dibutoxymethyl silicyl Propyl ester, acrylic acid diisopropoxy methyl silicane base propyl ester, acrylic acid dimethoxysilyl propyl ester, acrylic acid diethoxy Base silicyl propyl ester, acrylic acid dibutoxy silicyl propyl ester, acrylic acid diisopropoxy silicyl propyl ester, vinyl Pyridine, vinyl acetate, vinyl butyrate, vinyl benzoate, maleic anhydride, N-phenylmaleimide, N- butyl Malaysia Acid imide, n-vinyl pyrrolidone, N- vinyl carbazole and combinations thereof.This list is not exhausted.

Polymerizable monomer composition additionally comprises at least one cross-linking monomer at least two ethylenically unsaturated groups. Each of at least two ethylenically unsaturated groups of cross-linking monomer can undergo polymerization certainly.By tool, there are two polymerizable Ethylenically unsaturated group, it will be understood by those skilled in the art that cross-linking monomer will be in the polymer substrate molecule knot of polymeric beads Crosslinking points are provided in structure.

In one embodiment, cross-linking monomer has at least three ethylenically unsaturated groups.These three olefinics are unsaturated Each of group should also be as being polymerizable.

The important feature of cross-linking monomer used according to the invention is that at least two ethylenically unsaturated group is by least 4 A continuous non-annular atom separates.When cross-linking monomer has at least three ethylenically unsaturated groups, at least three olefinic is not By at least four, continuously non-annular atom separates each of saturated group.

It is separated by ethylenically unsaturated group by least " 4 continuous non-annular atoms ", it is intended that in ethylenically unsaturated group Between atom connection in must have the non-annular atom of at least four connection in sequential series.Pass through " non-annular atom ", it is intended that do not formed The atom of a part of ring structure.Property about non-annular atom does not limit specifically.For example, continuous non-annular atom can be with Including carbon atom, nitrogen-atoms, oxygen atom, or combinations thereof.

In one embodiment, at least two ethylenically unsaturated group is by least five or at least six or at least 7 A non-annular atom separates.

When cross-linking monomer includes at least three ethylenically unsaturated group, at least three ethylenically unsaturated group is respectively by extremely Few 4 or at least five or at least six or the non-annular atom of at least seven separate.

In a further embodiment, cross-linking monomer is acyclic cross-linking monomer.

The example of suitable cross-linking monomer at least two ethylenically unsaturated group includes but is not limited to glycol dinitrate Base acrylate, poly(ethylene glycol) dimethylacrylate, methylene-bisacrylamide (methylene Bisacrylamide), triethylene glycol diacrylate and triethylene glycol dimethacrylate, glycol diacrylate and Ethylene glycol dimethacrylate, diethylene glycol diacrylate and dimethacrylate, glycerol diacrylate Ester and glycerine dimethacrylate, 1,3 butyleneglycol diacrylate and 1,3 butylene glycol dimethylacrylate, 1,3- third Omega-diol diacrylate and 1,3- dimethacrylate, 1,3- Diacrylate and 1,3- pentanediol diformazan Base acrylate, 1,4 butanediol diacrylate and 1,4- butanediol dimethylacrylate, two propylene of hexamethylene glycol Acid esters and hexamethylene glycol dimethylacrylate, decamethylene omega-diol diacrylate and decamethylene glycol dimethyl propylene Olefin(e) acid ester, 2,2- dihydroxy methylpropane diacrylate and 2,2- dihydroxy methylpropane dimethylacrylate, tripropylene glycol two Acrylate and tripropylene glycol dimethylacrylate, (p-hydroxybenzene) the propane diacrylate of 2,2- bis- and 2,2- bis- are (right Hydroxy phenyl) propane dimethylacrylate, 2,2,4- trimethyl -1,3- Diacrylate and 2,2,4- trimethyl - 1,3- dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethylacrylate, and combinations thereof.

Suitable cross-linking monomer at least three ethylenically unsaturated groups includes but is not limited to trimethylolpropane tris Acrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythrite trimethacrylate acid Ester, glycerol tri-acrylate, glycerol trimethacrylate, pentaerythritol tetraacrylate, pentaerythrite tetramethyl acrylic acid Ester, three (2- hydroxyethyl) isocyanurate triacrylates, ethoxylated trimethylolpropane triacrylate, ethoxylation Trimethylol-propane trimethacrylate, propoxylation trimethylolpropane trimethacrylate, propoxylation trihydroxy methyl third Alkane trimethyl acrylic ester, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethyl acrylic ester, propoxylation are sweet Oily triacrylate, propoxylated glycerol trimethyl acrylic ester, ethoxylation pentaerythritol triacrylate, ethoxylation season Penta tetrol trimethyl acrylic ester, pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate trimethacrylate acid Ester, ethoxylation pentaerythritol tetraacrylate, ethoxylation pentaerythritol tetramethylacrylate, pentaerythritol propoxylate Tetraacrylate, pentaerythritol propoxylate tetramethyl acrylate, and combinations thereof.

Suitable cross-linking monomer at least three ethylenically unsaturated groups further include but be not limited to ethoxylation (3,6, 9,12,15,18 or 20) trimethylolpropane trimethacrylate, ethoxylation (3,6,9,12,15,18 or 20) trihydroxy methyl third Alkane trimethyl acrylic ester, propoxylation (3,6,9,12,15,18 or 20) trimethylolpropane trimethacrylate, propoxylation (3,6,9,12,15,18 or 20) trimethylol-propane trimethacrylate, ethoxylation (3,6,9,12,15,18 or 20) are sweet Oily triacrylate, ethoxylation (3,6,9,12,15,18 or 20) glycerol trimethacrylate, propoxylation (3,6,9, 12,15,18 or 20) glycerol tri-acrylate, propoxylation (3,6,9,12,15,18 or 20) glycerol trimethacrylate, second Oxygroup (3,6,9,12,15,18 or 20) pentaerythritol triacrylate, ethoxylation (3,6,9,12,15,18 or 20) season penta Tetrol trimethyl acrylic ester, propoxylation (3,6,9,12,15,18 or 20) pentaerythritol triacrylate, propoxylation (3, 6,9,12,15,18 or 20) pentaerythritol acrylate trimethyl, ethoxylation (4,5,8 or 16) pentaerythrite tetrapropylene acid Ester, ethoxylation (4,5,8 or 16) pentaerythritol tetramethylacrylate, propoxylation (4,5,8 or 16) pentaerythrite 4 third Olefin(e) acid ester, propoxylation (4,5,8 or 16) pentaerythritol tetramethylacrylate, and combinations thereof.

It will be understood by those skilled in the art that the number in the bracket after allcoxylated moiety refers to repeating alcoxyl above The number of base group.

Via the type for being suitble to cross-linking monomer used according to the invention is explained further, compare cross-linking monomer trihydroxy methyl Propane triacrylate and divinylbenzene will be convenient.Therefore, there are three olefinics for trimethylolpropane trimethacrylate tool Unsaturated group, described each 7 non-annular atoms of freedom of ethylenically unsaturated group separate.On the contrary, divinylbenzene be have only by The cross-linking monomer for two ethylenically unsaturated groups that annular atom separates.Therefore, the cross-linking monomer of such as divinylbenzene is fallen in suitable Except the range for closing cross-linking monomer used according to the invention.

In one embodiment, the polymerizable monomer composition that process according to the invention uses does not include divinyl Benzene.Correspondingly, in another embodiment, the polymer substrate of polymeric beads according to the present invention does not include or is not incorporated in two The polymerized monomer residue of vinyl benzene.

Other than polymerizable monomer composition, dispersed phase also includes solid particulate materials.When dispersed phase is described as point When scattered organic phase, it will be appreciated that, organic phase comprising solid particulate materials or will also disperse solid particulate materials Wherein.

In one embodiment, solid particulate materials are the types for leading to following polymeric beads: the polymeric beads tool Have than them otherwise there is no solid particulate materials by the higher density of the density having.Offer is provided Polymeric beads with increased density, it can be advantageous to reduce their sedimentation time, this allows polymeric beads from just by from Simpler separation in the water sample of reason.In this case, solid particulate materials can be described as weighting agent, and have Help promote the rapid subsidence of polymeric beads.

According to such embodiment, used solid particulate materials will be had than solid particle is being not present The material of the higher density of the density of polymeric beads in the case where material.Solid particulate materials will typically not dissolve in and be used to make Any liquid of standby polymeric beads, and typically it is also insoluble in any liquid that resulting polymers pearl can contact.

The example of suitable solid particulate materials includes but is not limited to titanium dioxide, zirconium oxide, barite, cassiterite, dioxy SiClx, aluminosilicate, nickel oxide, copper oxide, zinc oxide, zinc sulphide and other heavy metal oxide, sulfide, sulfuric acid Salt, carbonate.

In one embodiment, solid particulate materials are magnetic materials.

As used herein, be intended to indicate can be by the property of either temporarily or permanently magnetized substance for term " magnetic " Matter, and therefore including is paramagnetic property.Therefore, refer to that " magnetic-particle " or " magnetic retention granular materials " means this Substance can at least be magnetized, if not yet in magnetized state.

Solid magnetic particles material, which is incorporated into polymeric beads, can advantageously allow them to be used to be related to wait locate In the application of the solid stream of water of reason.In the case where any application shearing force is not present, magnetic-particle in polymeric beads it Between attraction cause they flocculate and rapid subsidence, this enables pearl easily to be divided under harsher process conditions From.

In order to make polymeric beads have magnetism, it is magnetic solid particulate materials that dispersed phase, which may include any,.It is such The example of material includes but is not limited to gamma-iron oxide (γ-Fe₂O₃, also referred to as maghemite), magnetic iron ore (Fe₃O₄), titanium dioxide Chromium, other metal oxides and more external magnetic material (exotic magnetic material), for example, based on neodymium or Those of samarium and other rare earth materials, such as samarium-cobalt or neodymium iron boride.Maghemite is preferably as it is cheap.It is magnetic Particle can be comprised in dispersed phase in the form that can be magnetized or can not be magnetized.

Suitable paramagnetic material includes but is not limited to iron-bearing mineral, such as montmorillonite, nontronite, biotite, siderite With pyrite, aluminium and copper.

The granularity of solid particulate materials can be the polymeric beads up to formed during this process granularity very One of size in the range of.It is likely difficult to be evenly dispersed in entire polymeric beads greater than the solid particle of the range.More Preferably, the size of solid particle is in the range of from sub-micron (such as 0.1 μm) to about 50 μm, such as from about 0.05 μm to about 10 μm, or from about 0.05 μm to 5 μm, or from about 0.05 μm to 1 μm.

It it may also be desirable to be used to for solid particulate materials being dispersed in dispersed phase using dispersing agent.Dispersing agent is used to particle It is dispersed in the drop of dispersed phase, with the stable dispersion (or suspension) to form particle in dispersed phase.Dispersing agent Also it is used to promote particle substantially uniform distribution in the polymer substrate for the polymeric beads being entirely thusly-formed.By with this Kind mode distributed granule, avoids or at least alleviates the erosion problem of the particle from polymeric beads in use, if Grain, which is only located on the outer surface of pearl, may then occur the problem.

Therefore, in one embodiment, dispersed phase additionally comprises dispersing agent, whole for being dispersed in solid particulate materials In a dispersed phase.Correspondingly, in a further embodiment, the polymer substrate of polymeric beads, which has, is distributed in dispersion therein Agent.

Suitable dispersing agent for dispersion solid particle material usually will have good combination parent to the surface of particle And power, and preferably can should chemically or physically be integrated to the surface of particle.Dispersing agent usually will also with it is polymerizable Monomer composition and the polymer substrate being thusly-formed are compatible or dissolve in polymerizable monomer composition and be thusly-formed In polymer substrate.

In one embodiment, dispersing agent and the monomer reaction of polymerizable monomer composition with become to be covalently bond to as This polymer substrate formed.Correspondingly, in a further embodiment, the polymer substrate of polymeric beads has covalent bond To its dispersing agent.In this case, dispersing agent will be not only distributed only in entire polymer substrate, but be polymerize being formed A part of object matrix.

Using the dispersing agent for forming covalent bond with polymer substrate particle is not only resulted in entire polymeric beads substantially Uniform distribution, and by the way that dispersing agent is covalently bound to polymer substrate, particle additionally advantageously becomes more effectively to combine In pearl.In such a case, it is possible to avoid the problem that or at least mitigate particle leaching from polymeric beads.

The selection of dispersing agent will typically depend on used specific granular materials and polymerizable monomer composition.Ability Field technique personnel should can be readily selected suitable dispersing agent according to the particular agent used in preparation pearl.

The example of suitable dispersing agent for solid particulate materials to be dispersed in dispersed phase includes but is not limited to that amine is embedding Section copolymer, such as by Byk Chemie with trade name162、163、 164、166 HesThose of 167 sales.It is the discovery that suitable other kinds of dispersing agent packet Include polyethers phosphate and modified polyurethane.Other suitable dispersing agents include Solsperse 20000 from Lubirzol, Solsperse 24000、Solsperse 32000、Solsperse 38500、Solsperse 46000、Solsperse 82500 and Solsperse 55000.By Huntsman sale305 Hes40PF, it is sold by Cognis It sellsAP12, AP60 and AP69, it is sold by the EFKA PU 4063 of BASF sale, by Kusumoto Chemicals Disparlin DA-375, by Henkel saleIt AEP8100 and AEP5300 and is sold by Rhodia 'sWith

Weight based on polymerizable monomer composition, solid particulate materials usually will be with the amounts from 10wt% to 300wt% It is added into, such as from 20wt% to 100wt% (identical basis).When it is present, it based on the weight of solid particulate materials, is used for Solid particulate materials, which are dispersed in the dispersing agent in dispersed phase usually, to be added into the amount from 0.1wt% to 30wt%, such as With the amount from 1wt% to 10wt%.

Dispersed phase additionally comprises non-polymer pore-foaming agent and does not include non-polymer pore-foaming agent.

Pore-foaming agent be used to assign internal macroporosity and surface macroporosity in the art.Promote the such of polymeric beads Porosity increases the total surface area of pearl, this can improve the efficiency that pearl removes certain pollutants from water again.

Pore-foaming agent is classified as non-polymer or polymer in which can be convenient.Polymer pore-foaming agent is typically via poly- It closes technique to be made, and the molecular structure with the polymeric residues based on monomer.Non-polymer pore-foaming agent typically has than poly- Object pore-foaming agent lower molecular weight is closed, is not and not have the polymeric residues based on monomer made of polymerization technique Molecular structure.

Pore-foaming agent is not involved in the zone of dispersion of polymerization reaction and works by providing in polymerizable monomer composition.In Occur to polymerize and formed after polymer substrate, pore-foaming agent can be partially or even wholly removed, thus in the structure of pearl In leave hole or gap.

Although non-polymer pore-foaming agent usually for example fully can be gone out polymeric beads structure by cleaning, It is some polymer pore-foaming agents at least due to their high molecular weight, can for good and all be captured in the polymeric beads being thusly-formed In.

It is prepared for using non-polymer pore-foaming agent, polymer pore-foaming agent and combinations thereof for removing pollutant from water Polymeric beads.

Use the non-polymer pore-foaming agent combined with divinylbenzene as crosslinking for example, WO 1996/007675 is disclosed The polymeric beads of monomer preparation.

WO 2014/032092 is disclosed using polymer pore-foaming agent and similar to cross-linking monomer as described herein preparation Polymeric beads.It is said that providing the poly- of the polymer pore-foaming agent with retention using the combination of cross-linking monomer and polymer pore-foaming agent Close object pearl, the polymeric beads have unique dimpled surface, relative to disclosed in WO 1996/007675 those, institute It states dimpled surface and shows the improved property for the removal pollutant from water.

Surprisingly, relative to polymeric beads disclosed in WO 96/07675 or WO 2014/032092, according to this hair The polymeric beads of bright preparation can show improved engineering properties, such as improved wearability and/or improved for from water The middle ability for removing pollutant.Without wishing to be bound by theory, it is believed that, use specified cross-linking monomer and non-polymer The combination of pore-foaming agent and there is no polymer pore-foaming agent, provides specific form for the polymer substrate of polymeric beads, this order People surprisingly enhances wearability and/or pollutant such as DOC from the removal in water.Pass is provided in following Examples part In the other discussion of these points.

The example for the non-polymer pore-foaming agent that can be used according to the present invention includes aromatic compounds such as toluene and benzene, alcohol Such as butanol, isooctanol, cyclohexanol, lauryl alcohol, isoamyl alcohol, tert-pentyl alcohol and methyl isobutyl carbinol, ester such as ethyl acetate and Butyl acetate, saturated hydrocarbons such as normal heptane, isooctane, halogenated solvent such as dichloroethanes and trichloro ethylene and plasticizer example Such as dioctyl phthalate and dibutyl adipate, and combinations thereof.

The example for the polymer pore-foaming agent not used according to the present invention including but not limited to poly- (vinyl methyl ether) is gathered (ethylene oxide), poly- (vinyl acetate), poly- (methyl methacrylate), poly- (vinyl acetate is total to maleic acid and ester or rich horse Acid and ester), alcohol ethoxylate, fatty alcohol alkoxy compound, alcohol alkoxylates (alcohol alkoxylate), rouge Fat acid ethoxylate, castor oil ethoxylate, amine ethoxylates, alkylphenol ethoxylate, alkyl ethoxy Carboxylic acid, and combinations thereof.

Relative to the total amount of used non-polymer pore-foaming agent and monomer, non-polymer pore-foaming agent usually will be from about Amount in the range of 10wt% to about 60wt%, or with the amount in the range of from about 15wt% to about 60wt%, or from about Amount in the range of 20wt% to about 50wt% is used.

According to the present invention, non-polymer pore-foaming agent is not used in combination with any polymer pore-foaming agent.

Component in dispersed phase is typically formed immixture.In other words, at least polymerizable monomer composition, solid Granular materials and non-polymer pore-foaming agent are thoroughly mixed.

After providing dispersion, technique of the invention includes polymerizeing polymerizable monomer composition to form polymer Pearl.Polymerization may need the presence of radical initiator to cause the reaction of monomer.In this case, radical initiator It may be embodied in dispersed phase.It will be understood by those skilled in the art that initiator ready for use will depend on existing polymerizable list The property of body.It is only used as example, suitable initiator includes azo isobutyronitrile, benzoyl peroxide, lauroyl peroxide and uncle Butylhydroperoxide.

Based on the total weight of existing polymerisable monomer, the amount of the initiator used is usually in 0.01wt% to 5wt%, more In the range of preferably 0.10wt% to 1wt%.

Technique of the invention can be used conventional suspension polymerization technique and carry out.In this case, (it includes dispersed phase It is monomer to be polymerized) dispersion in continuous phase typically via mixing such as organic phase and water phase and shears gained mixture To realize.The adjustable shearing force for being applied to dispersion, to control the size of the drop of dispersed phase.When the drop quilt of dispersed phase When polymerization is to generate polymeric beads, the shearing force for being applied to dispersion largely controls the granularity of polymeric beads.

In general, polymeric beads are controlled so as to have in the range of about 10 microns to about 500 microns, or for example micro- about 30 In the range of 1,000 micron of meter Zhi Yue, or granularity in the range of about 100 microns to about 300 microns.

After stabilising dispersions of the dispersed phase in continuous phase are established, polymerization reaction can be by heating dispersion Cause to desired reaction temperature.Dispersion can be maintained at desired reaction temperature, until polymerization reaction is substantially complete At.

In carrying out polymerization reaction, monomer is typically selected to provide the polymeric beads for being suitble to desired application.For example, Depending on used monomer, resulting polymers pearl may include acid groups or amine groups, polymeric beads can be enable to rise To the effect of ion exchange resin, and these functional groups are directly provided by the polymeric residues of one or more of functional monomers.

Amine functional group directly can be introduced the functional monomer of pearl includes but is not limited to dimethylamine second Ester, aminopropyl acrylamide and Methacrylamide, N, N- dimethylaminopropylacryl amide and Methacrylamide, second Alkenyl pyridine and organic-soluble diallylamine or vinyl imidazole salt.

Acid functional group directly can be introduced the functional monomer of pearl includes but is not limited to acrylic acid, methacrylic acid and ethyl Acrylic acid (ethacrylic acid).

Selectively, after the polymerization is complete, resulting polymers pearl may need subsequent processing to provide functional group, the official Can roll into a ball will make polymeric beads can be used as ion exchange resin.Particular procedure technique used will depend on polymer to be processed The composition of pearl.Treatment process may include make polymeric beads with by one of functional group conversions' ion-exchange group present on pearl Kind or more compound reaction, or make functional group on pearl and ion-exchange group introduced to the one or moreization of pearl Close object reaction.

Functional group on pearl is converted into the treatment process of ion-exchange group, and functional group can be converted into amido Group or acid groups or its salt or quaternary ammonium group.For this purpose, the various combinations of suitable functional group and reactant can be used, Its property will be known to the skilled in the art.In this case, it is preferable that the functional group on pearl be amide group or Ester group, and amide group or ester group are introduced into polymeric beads via Amide functional monomers or ester functional monomer.

Exemplary of amides functional monomer includes but is not limited to N- vinyl formamide or N- methyl-Nvinylacetamide. Amide group can easily be turned by hydrolysis, Hofmann degradation (Hofmann degradation) or borohydride reduction It is melted into amine groups.Hydrolysis is preferred technology.For example, in N- vinyl formamide or N- methyl-Nvinylacetamide monomer Amide group in unit can be converted into amine groups by hydrolysis.Amine groups can be readily converted into salt or quaternary ammonium group Group.

Exemplary ester functional monomer includes but is not limited to methyl acrylate, ethyl acrylate or butyl acrylate.Ester group Weak acid group can be readily converted by hydrolysis.For example, in methyl acrylate, ethyl acrylate or butyl acrylate list Ester group in body unit can be converted into weak acid group by hydrolysis.

In the one or more of chemical combination for making the functional group on pearl with the functional group comprising ion-exchange group to be introduced to pearl In the technique of object reaction, which is preferably introduced amine groups or quaternary ammonium group.For this purpose, can adopt With the various combinations of suitable functional group and compound of reaction, property will be known to the skilled in the art.

In this case, the functional group on pearl can include but is not limited to halogen, epoxides, ester and amide.In this way Functional group can be introduced into polymeric beads via suitable functional monomer.Exemplary functional monomer for the purpose include but It is not limited to vinyl chloride (vinyl benzyl chloride), glycidyl methacrylate, acrylate or methyl Acrylate or amide (as defined above).Such functional group can be anti-with the compound of introducing amine groups or quaternary ammonium group It answers.Suitable reactant compound includes but is not limited to amine, diamines and polyamines compound and its respective salt.

Preferred compound for introducing amine groups or quaternary ammonium group includes but is not limited to piperidines, N, N- diethyl second two Amine, dimethylamine, diethylamine, trimethylamine, triethylamine, 3- dimethylamino propylamine, ethylenediamine, diethylenetriamines, polyethyleneimine Amine and its respective salt.

After the polymerization is complete, non-polymer pore-foaming agent can be retained in gap/hole of the polymer substrate of polymeric beads In gap.For the ease of removing non-polymer pore-foaming agent residue and other reaction residues from polymeric beads, it may be necessary to make Pearl is subjected to cleaning procedure.This can be realized by a series of washing steps and/or by stripping pearl.

It is a kind of for cleaning the method for polymeric beads the following steps are included:

(a) polymeric beads are added in big excessive water, stir and allow to settle, pearl is then separated from supernatant；

(b) step (a) is repeated several times；

(c) optionally water washed pearl is dispersed in alcohol (such as ethyl alcohol)；

(d) pearl and drying are separated from alcohol.

Selectively, polymeric beads can be first subjected to strip, and then be washed as described above.

Therefore, in one aspect, the present invention provides polymeric beads, the polymeric beads include porous polymer matrix, The porous polymer matrix, which has, is distributed in solid particulate materials therein, and the polymer substrate (i) includes below poly- Close monomer residue: (a) at least one single ethylenically unsaturated monomer and (b) at least one cross-linking monomer, at least one crosslinking Monomer has by least four at least two ethylenically unsaturated groups that continuously non-annular atom separates, wherein the polymer matrix Matter includes non-polymer pore-foaming agent and does not include polymer pore-foaming agent.

After making the polymeric beads being thusly-formed be subjected to cleaning, any remaining non-polymer pore can be removed Agent.

In this case, invention additionally provides polymeric beads, the polymeric beads include porous polymer matrix, The porous polymer matrix, which has, is distributed in solid particulate materials therein, and the polymer substrate (i) includes below poly- Close monomer residue: (a) at least one single ethylenically unsaturated monomer and (b) at least one cross-linking monomer, at least one crosslinking Monomer has by least four at least two ethylenically unsaturated groups that continuously non-annular atom separates, wherein the polymer matrix Matter does not include pore-foaming agent.

To avoid any query, by the inclusion of the polymer substrate of " polymerized monomer residue ", it is intended that specified monomer is Polymerization is to form polymer substrate, and therefore polymerized monomer residue constitutes at least one of the molecular structure of the polymer substrate Point.In other words, polymer substrate (i) provides at least part of polymerized monomer residue below as its molecular structure: (a) At least one list ethylenically unsaturated monomer and (b) at least one cross-linking monomer, at least one cross-linking monomer have by least 4 At least two ethylenically unsaturated groups that a continuous non-annular atom separates.

Therefore, polymeric beads according to the present invention are formed by porous polymer matrix, polymer substrate itself (i) provide with Under a part as its molecular structure of polymerized monomer residue: (a) at least one single ethylenically unsaturated monomer and (b) at least one Kind cross-linking monomer, at least one cross-linking monomer have by least four at least two olefinics that continuously non-annular atom separates Unsaturated group, and (ii) have be distributed in solid particulate materials therein.

In one embodiment, polymeric beads have ion-exchange capacity or provide ion exchange energy after experience reaction Power.In this case, polymer substrate include (or by formed below) below: the polymerization list of one or more of functional monomers Body residue, the functional monomer have the functional group for the ion exchange site for providing or providing polymeric beads after the reaction.

The polymerized monomer residue of one or more of functional monomers can actually be that at least one monoene belongs to unsaturated single The polymerized monomer residue of body and/or at least one cross-linking monomer.

The present invention also provides the method for processing aqueous solution (such as water), this method includes making the aqueous solution and the present invention Polymeric beads or polymeric beads prepared in accordance with the present invention contact.The processing of aqueous solution may include removal pollutant, such as DOC.In this case, DOC becomes the surface for being adsorbed to polymeric beads, and removing polymer pearl is also led from aqueous solution DOC is caused to be removed from aqueous solution.

Invention additionally provides the methods that ion is separated from aqueous solution, and the method includes making solution and have ion The polymeric beads of the invention of exchange capacity or polymeric beads prepared in accordance with the present invention contact.In this case, ion becomes At the surface for being adsorbed to polymeric beads, and ion is also resulted in from aqueous solution from removing polymer pearl in aqueous solution and is divided From.

Polymeric beads can be separated easily from aqueous solution together with pollutant/ion of absorption, to leave purifying Aqueous solution.Since polymeric beads include solid particulate materials, they can increase from the separation in aqueous solution for example, by having The pearl of the density added promotes, and the increased density allows sedimentation faster.Selectively, polymeric beads may include magnetism Solid particulate materials, and they can use the magnetic properties of pearl and are separated from solution.For example, there is no shearing forces In the case of, pearl can be assembled by magnetic pull, and be settled from the solution of purifying.Selectively, they can be in wet type height It is separated on intensity magnetic separator or magnetic drum separator or similar device.

The example for the anion that can be separated from aqueous solution includes but is not limited to the organic matter dissolved, such as humic acid group With fulvic acid root, chromate, arsenate, arsenous anion, selenate radical, selenite radical, phosphate radical, perchlorate, nitrate anion and molten Solve organic nitrogen.

The example for the cation that can be separated from aqueous solution includes but is not limited to transition metal ions, such as cadmium and zinc, And there are also metal ion such as calcium and magnesium.

Polymeric beads according to the present invention from aqueous solution especially suitable for removing unacceptable pollutant.

Therefore, the present invention also provides the method for removing DOC from aqueous solution, this method includes that (i) makes the aqueous solution It is contacted with polymeric beads of the invention or polymeric beads prepared in accordance with the present invention, and (ii) is removed from aqueous solution and inhaled thereon Polymeric beads with DOC, to remove DOC from aqueous solution.

Therefore, the present invention also provides from aqueous solution remove ion method, the method includes (i) make it is described water-soluble Liquid is contacted with ion-exchange polymer pearl of the invention or ion-exchange polymer pearl prepared in accordance with the present invention, and (ii) from The polymeric beads that experienced ion exchange with ion to be removed are removed in the solution.

Relative to conventional polymeric beads, such as according to those of WO 96/07675 or WO 2014/032092 preparation, root The increase of the charge density of about 10%-20% can be advantageously provided according to polymeric beads of the invention.

Polymeric beads according to the present invention advantageously show excellent wearability, thus make they during application for example It is minimized from the abrasion removed in aqueous solution in unacceptable pollutant.

Term " alkyl " include saturation aliphatic group, including linear alkyl groups (for example, methyl, ethyl, propyl, Butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl etc.) and branched alkyl group (isopropyl, tert-butyl, isobutyl group Deng).In some embodiments, " alkyl " refers to straight chained alkyl.Wording " C_x-yAlkyl ", wherein x is 1-5 and y is 2- 12, indicate the alkyl group (linear chain or branched chain) containing specified carbon atom number.For example, wording C_1-2Alkyl includes but is not limited to Methyl, ethyl, propyl, butyl, isopropyl, tert-butyl and isobutyl group.Term " alkylidene " refers to divalent alkyl group.

In one embodiment, linear or branched alkyl group has 12 or less carbon atom (i.e. C_1-12).Some In embodiment, linear or branched alkyl group has 8 or less carbon atom (i.e. C_1-8)。

Term " alkenyl " includes unsaturated aliphatic group, and above-described alkane is similar in length and possible substitution Base, but it contains at least one double bond.For example, term " alkenyl " includes straight-chain alkenyl group (for example, vinyl, acrylic, fourth Alkenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base etc.) and branched alkenyl group.In some embodiment party In case, " alkenyl " refers to straight-chain alkenyl.In certain embodiments, linear chain or branched chain alkenyl group has 12 in its main chain A or less carbon atom is (for example, be C for straight chain₂-C₁₂, it is C for branch₃-C₁₂).Term C₂-C₁₂Including containing 2 extremely The alkenyl group of 12 carbon atoms.Term " alkenylene " refers to divalent alkenyl group.

Term " alkynyl " includes unsaturated aliphatic group, and above-described alkane is similar in length and possible substitution Base, but it contains at least one three key.For example, term " alkynyl " includes straight-chain alkynyl groups (such as acetenyl, propinyl, fourth Alkynyl, pentynyl, hexin base, heptynyl, octynyl, n-heptylacetylene base, decynyl etc.) and branched alkynyl group.In some embodiment party In case, " alkynyl " refers to straight-chain alkynyl.In certain embodiments, linear chain or branched chain alkynyl group has 12 in its main chain A or less carbon atom is (for example, be C for straight chain₂-C₁₂, it is C for branch₃-C₁₂).Term C₂-C₁₂Including containing 2 extremely The alkynyl group of 12 carbon atoms.Term " alkynylene " refers to divalent alkynyl radical group.

Term " carbocylic radical " includes any non-aromatic monocyclic, polycyclic, condensed or conjugation hydrocarbon residue, preferably C_3-20(such as C_3-10Or C_3-8).These rings can be saturation, such as naphthenic base, or can have one or more double bonds (cycloalkenyl) And/or one or more three keys (cycloalkynyl radical).Particularly preferred carbocyclyl moieties are 5 yuan, 6 yuan or 9-10 ring system.It closes Suitable example include cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, Cyclohexenyl group, cyclo-octene base, cyclopentadienyl group, cyclohexadienyl, cyclooctatetraenyl, indanyl, decahydro naphthalene and indenyl.Carbocyclic ring Base group is optionally replaced by one or more optional substituent groups as herein defined.Term " sub- carbocylic radical (carbocyclylene) " it is intended to indicate the bivalent form of carbocylic radical.Term " naphthenic base " includes saturated cyclic aliphatic group (ring Propyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl).Term C_3-6Naphthenic base includes but is not limited to cyclopropyl, cyclopenta and ring Hexyl.Again it is preferred to naphthenic base have in its ring structure from 4-7 carbon atom, and more preferably have in ring structure There are 5 or 6 carbon atoms.As used herein, term " Heterocyclylalkyl " is referred to comprising one or more interior ring hetero atoms Group of naphthene base.Equally, cycloalkenyl groups can have in its ring structure and exist from 3-8 carbon atom, and more preferably There are 5 or 6 carbon atoms in ring structure.

Term " hetero atom " includes the atom of any element different from carbon or hydrogen.Preferred hetero atom be nitrogen, oxygen, sulphur with And phosphorus.Particularly preferred hetero atom is nitrogen and oxygen.

Term " amine " or " amino " should be understood to be widely used in molecule or part or functional group, as led in this field It understands, and can be primary, secondary or tertiary.Term " amine " or " amino " include wherein nitrogen-atoms be covalently bound at least one The compound of a carbon or hydrogen.

As used herein, term " being optionally substituted " typically refers to the hydrogen atom on group by non-hydrogen-based The case where group replaces.Unless the context otherwise requires, such as in the case where clearly referring to optional substituent group, otherwise appoint The example of the substituent group of choosing is described below.Any group being optionally substituted can have one, two, three or more A optional substituent group.

In some embodiments, optional substituent group is selected from: the C being optionally substituted_1-6Alkyl；It is optionally substituted C_6-10Aryl；The C being optionally substituted_2-8Heterocycle；Halogen；-OH；-NH₂；-NO₂；-SO₂NH₂；-COOH；-COO(C_1-6Alkane Base)；-NHCOO(C_1-6Alkyl)；-NH-COR^aWherein R^aIt is H or C_1-6Alkyl；-NR^aR^bWherein R^aIt is H or C_1-6Alkyl and R^bIt is H or C_1-6Alkyl；-C(O)NR^aR^b, wherein R^aIt is H or C_1-6Alkyl and R^bIt is H, C_1-6Alkyl；-C(O)R^aWherein R^aIt is H or C_1-6 Alkyl；Or-Y-Q is wherein:

Y is selected from :-O- ,-NH- ,-N (C_1-6Alkyl)-,-NHSO₂-、-SO₂NH-、-NHCONH-、-NHCON(C_1-6Alkane Base)-,-S (O)_qWherein q is 0,1 or 2 ,-C (O) NH- ,-C (O) N (CH₃- NHC)-, (O)-,-C (O)-,-NHC (NH) NH-, or It is not present, and

Q is selected from: the C being optionally substituted_6-10Aryl；The C for the 5-10 member being optionally substituted_1-9Heteroaryl；Optionally by The C of substituted 3-10 member_1-9Heterocycle；The C being optionally substituted_3-10Naphthenic base；The C being optionally substituted_1-6Alkyl；Optionally Substituted C_1-6Alkyl acyl；The C being optionally substituted_2-6Alkenyl；The C being optionally substituted_2-6Alkynyl；And hydrogen.

In other embodiments, optional substituent group is selected from: the C being optionally substituted_1-6Alkyl；It is optionally substituted C_6-10Aryl；Halogen；-OH；-NH₂；-COOH；-COO(C_1-6Alkyl)；-NR^aR^bWherein R^aIt is H or C_1-6Alkyl, and R^bIt is H Or C_1-6Alkyl；-NH-COR^aWherein R^aIt is H or C_1-6Alkyl；-C(O)NR^aR^b, wherein R^aIt is H or C_1-6Alkyl, and R^bBe H, C_1-6Alkyl；C(O)R^aWherein R^aIt is H or C_1-6Alkyl；Or-Y-Q, in which:

Y is selected from :-O- ,-NH- ,-N (C_1-6Alkyl)-,-NHCONH- ,-S- ,-C (O) NH- ,-C (O) N (CH₃)-、-NHC (O)-,-C (O)-,-NHC (NH) NH-, or be not present, and

Q is selected from: the C optionally replaced by-OH_6-10Aryl；The C of 5-10 member_1-9Heteroaryl；The C of 3-10 member_1-9Heterocycle； C_3-10Naphthenic base；C_1-6Alkyl；C_1-6Alkyl acyl；C_2-6Alkenyl；C_2-6Alkynyl；And hydrogen.

Term " amide ", " acylamino- " or " amino carbonyl " includes the compound containing nitrogen-atoms or part, the nitrogen-atoms In conjunction with the carbon of carbonyl or thiocarbonyl group.

Term " aryl " refers to that aromatic monocyclic (such as phenyl) or polycyclic moiety are (such as tricyclic, bicyclic, such as naphthalene, anthracene Base, phenanthryl).Aryl group can also with non-aromatic alicyclic ring or heterocyclic fused or bridge joint, it is polycyclic (for example, tetrahydro to be formed Naphthalene, methylenedioxyphenyl base).

As used in this article, term " heteroaryl " represents the monocycle typically in each ring with up to 7 atoms Or it is bicyclic, wherein at least one ring is aromatics and includes from 1 to 4 selected from the hetero atom by O, N and S group formed. Heteroaryl groups within the scope of this definition include but is not limited to: benzimidazole (benzimidazole) (further referred to as benzo miaow Azoles (benzoimadazole)), acridinyl, carbazyl, cinnoline base, quinoxalinyl, pyrazolyl, indyl, benzotriazole base, furan It mutters base, thienyl, benzothienyl, benzofuranyl, quinolyl, isoquinolyl, oxazolyl, isoxazolyl, indyl, pyrazine Base, pyridazinyl, pyridyl group, pyrimidine radicals, pyrrole radicals, tetrahydroquinoline.Such as the definition of hereafter heterocycle, " heteroaryl " is also understood to N- oxide derivative including any nitrogenous heteroaryl.Heteroaryl substituent be bicyclic and a ring be it is non-aromatic or Without in heteroatomic situation, it should be understood that attachment is via aromatic ring or via containing heteroatomic ring respectively.

As used herein term " heterocycle " or " heterocycle " mean containing being selected from by O, N and S group from 1 to 4 At group heteroatomic 5 yuan to 10 yuan of aromatics or non-aromatic heterocycle, and including bicyclic radicals.Therefore, " heterocycle " Including above-mentioned heteroaryl and its dihydro and tetrahydro analog.The other examples of " heterocycle " include but is not limited to following: benzo Imidazole radicals, benzofuranyl, benzofuraxan base, benzopyrene oxazolyl, benzotriazole base, benzothienyl, benzoxazolyl, carbazole Base, carboline base, cinnoline base, furyl, imidazole radicals, indoline base, indyl, indolizine base (indolazinyl), the different benzene of indazolyl And furyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthopyridine base, epoxy ethyl, oxadiazoles base, oxazole Base, oxazoline, isoxazoline, oxetanyl, pyranose, pyrazinyl, pyrazolyl, pyridazinyl, pyridopyridine base, pyridazine Base, pyridyl group, pyrimidine radicals, pyrrole radicals, quinazolyl, quinolyl, quinoxalinyl, THP trtrahydropyranyl, tetrazole radical, tetrazolo pyridine Base, thiadiazolyl group, thiazolyl, thienyl, triazolyl, azelidinyl, 1,4- dioxanes base, hexahydroazepine base, piperazinyl, Piperidyl, pyridin-2-ones base (pyridin-2-onyl), pyrrolidinyl, morpholinyl, thio-morpholinyl, dihydrobenzo imidazole radicals, Dihydro benzo furyl, dihydrobenzo thienyl, dihydrobenzo oxazolyl, dihydrofuryl, glyoxalidine base, indoline Base, dihydro-isoxazole base, dihydro isothiazolyl, dihydro oxadiazoles base, dihydro-oxazole base, dihydro pyrazine base, pyrazoline base, two Pyridinium hydroxide base, dihydro-pyrimidin base, pyrrolin base, dihydroquinoline base, dihydro tetrazole radical, thiodiazoline base, dihydro-thiazolyl, Dihydrothiophene, dihydro triazolyl, dihydro azelidinyl, methylenedioxyphenyl formoxyl, tetrahydrofuran base and tetrahydro thiophene Pheno base and its N- oxide.The attachment of heterocyclyl substituent can occur via carbon atom or via hetero atom.As mentioned herein And " Heterocyclylalkyl " refer to saturated heterocyclyl group.In some embodiments, heterocycloalkyl is optionally by one Or more OH and/or CH₂OH replaces.The example of such group is simple sugars ribose." alkyl heterocycle as mentioned in this article Base " refers to the alkyl group for being attached to heterocyclyl groups.

Term " acyl group " includes containing carboxyl groups (CH₃CO-) or the compound of carbonyl group and part, such as CH₃CH₂CH₂CO-。

Term " alkoxy " includes substituted and unsubstituted alkyl, alkenyl and the alkynyl being covalently attached with oxygen atom Group.The example of alkoxy base includes methoxyl group, ethyoxyl, isopropoxy (isopropyloxy) (isopropoxy (isopropoxy)), propoxyl group, butoxy and amoxy group, and may include cyclic group such as cyclopentyloxy.

Term " carbonyl " or " carboxyl " include the carbon compound comprising connect with oxygen atom with double bond and partially and its mutual Become isomeric form.The example of part comprising carbonyl includes aldehyde, ketone, carboxylic acid, amide, ester, acid anhydrides etc..Term " carboxy moiety " or " carbonyl moiety " refers to group such as below: " alkyl-carbonyl " group, wherein alkyl group is covalently bound to carbonyl group； " alkenyl carbonyl " group, wherein alkenyl group is covalently bound to carbonyl group；" alkynylcarbonyl groups " group, wherein alkynyl group is covalent It is integrated to carbonyl group；" aryl carbonyl " group, wherein aryl group is covalently attached to carbonyl group.In addition, the term also refers to Be group that one of them or more hetero atom is covalently bound to carbonyl moiety.For example, the term include such as with Under part: amino carbonyl part (wherein nitrogen-atoms is integrated to the carbon of carbonyl group, such as amide)；Amino carbonyl oxygroup portion Point, wherein both oxygen and nitrogen-atoms are incorporated into the carbon (for example, being also known as " carbamate ") of carbonyl group.In addition, also Carbonyl including amino carbonyl amino group (such as urea) and in conjunction with hetero atom (such as nitrogen, oxygen, sulphur etc.) and carbon atom Other combinations of group.In addition, hetero atom can also be by one or more alkyl, alkenyl, alkynyl, aryl, aralkyl, acyl group Replace Deng part.

Term " thiocarbonyl " or " thiocarboxyl group " include the carbon compound comprising being connect with double bond with sulphur atom and portion Point.Term " thiocarbonyl moiety " includes the part similar to carbonyl moiety.For example, " thiocarbonyl " partially includes aminothio Carbonyl, wherein amino group is integrated to the carbon atom of thiocarbonyl group, in addition, other thiocarbonyl moieties include that oxygroup is thio Carbonyl (oxygen is integrated to carbon atom), aminocarbonothioylamino group etc..

Term " ester " includes containing the carbon or heteroatomic compound that are bonded to oxygen atom and part, the oxygen atoms bond In the carbon of carbonyl group.Term " ester " includes alkoxycarbonyl group, such as methoxycarbonyl, ethoxy carbonyl, propoxyl group carbonyl Base, butoxy carbonyl, pentyloxy carbonyl etc..Alkyl, alkenyl or alkynyl group are as defined above.

Term " hydroxyl (hydroxy) " or " hydroxyl (hydroxyl) " include the group with-OH.

Term " halogen " includes fluorine, chlorine, bromine and iodine.In some embodiments, halogen refers to fluorine or chlorine.

Term " polycyclic group " or it is " polycyclic " include have two or more rings (for example, naphthenic base, cycloalkenyl, cycloalkynyl radical, Aryl and/or heterocycle) part, two of them or more carbon is that two adjacent rings are shared, for example, ring is " thick Ring ".It is referred to as " bridge " ring by the ring that non-conterminous atom connects.

It should be appreciated that all compounds of the invention will also include as met the chemical valence of each atom needed for it is adjacent Key between atom and/or hydrogen.That is, double bond and/or hydrogen atom are typically added into following kind of atom Each provide following number generic key: carbon: four keys；Nitrogen: three keys；Oxygen: two keys；And sulphur: two, four or six A key.It is to be further understood that the definition for giving the variable of general formula described herein will generate and define and know with standard organic chemical Know (such as chemical valence rule) consistent molecular structure.

It should be noted that the structure of some compounds of the invention includes asymmetric carbon atom.It is therefore understood that It is, by such asymmetric isomers generated (for example, all enantiomters, stereoisomer, rotational isomer, interconversion Isomers, diastereoisomer or racemic modification) all it is included within the scope of the disclosure.Such isomers can pass through classics Isolation technics and by zinc bromide synthesis obtain in a substantially pure form.In addition, the knot discussed in this application Structure and other compounds and part further include its all tautomer.Compound described herein can by this field The synthetic strategy known obtains

The present invention will be further described with reference to non-limiting embodiment below.

Embodiment