CN100448900C - Styrene-isopropylene phosphonic acid copolymer - Google Patents
Styrene-isopropylene phosphonic acid copolymer Download PDFInfo
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Abstract
The process of free radical copolymerizing styrene and isopropenyl phosphonic acid in solution to synthesize styrene-isopropenyl phosphonic acid copolymer includes dissolving isopropenyl phosphonic acid and benzoyl peroxide or azo diisobutyronitrile in tetrafuran or other solvent, heating to 60-90 deg.c and dropping styrene to react for 6-16 hr; distilling out solvent, washing with distilled water, separating out water phase to obtain colloidal substance, and stoving to obtain styrene-isopropenyl phosphonic acid copolymer. The prepared styrene-isopropenyl phosphonic acid copolymer may be used in preparing (styrene-isopropenyl phosphonic acid)-inorganic phosphoric acid mixed salt as one new kind of organic-inorganic composite material, and may be further modified chemically to prepare new inorganic-organic composite functional high molecular material of different structures and uses.
Description
Technical field
The present invention relates to a kind of new function material, new catalyst precursor, be specifically related to the synthetic of styrene-isopropylene phosphonic acid (isopropenyl phosphonic acid) multipolymer.
Background technology
Along with the develop rapidly and the progress of science and technology, the scientific worker seeks to have new features in continuous exploration, the functional high molecule material of new function.Because polystyrene and benzene feedstock ethene thereof is inexpensive, be easy to get, therefore suitability for industrialized production, is the widest functional high molecule material carrier of purposes in numerous functional high molecule material precursors and carrier.Polystyrene can synthesize different purposes, functional polymer various in style by polymer chemistry reaction.Wherein, various ion exchange resin, resin, polymer reactant and polymer catalyst comprise that transition-metal coordination complex catalyst that polymer is immobilized and the immobilized chiral catalyst of polymer are several big key areas in the functional polymer research.In recent years, the applied research in organic synthesis of polymer reactant and polymer catalyst has obtained fast development.Therefore the development of new functional materials comprises that novel ion exchange resin, novel chelate resin, novel high polymer reagent and novel high polymer catalyzer and new functional macromolecule material precursor are the hot research problems that scientific workers extremely pay close attention to, these hot research problems not only have important significance for theories and learning value, and have broad application prospects and huge potential economic benefit.
The precursor or the carrier of functional polymers such as ion exchange resin, resin, polymer reactant and polymer catalyst commonly used have three classes:
1. inorganic carrier such as gac, silica gel, aluminium sesquioxide etc.
2. the organic polymer carrier then is that chloromethylated polystyrene resin and other have the resin of latent functionalization.
3. the polysiloxane of haloalkyl containing functional group side chain can be regarded as the inorganic organic polymer functionalization precursor or the carrier that have aforementioned both functions concurrently.
Layered phosphates is as inorganic functional material and inorganic-organic complex function material, research as inorganic ion exchanger, sorbent material, gas-chromatography weighting agent, new catalyst or support of the catalyst starts from the eighties, still belong to the exploratory stage at present, comparatively sophisticated functional materials is also few in number.
The inventor's seminar carries out the research of the organic and inorganic mixed phosphate of functionalization the earliest at home, focuses on the research of mixed phosphate zirconates catalyzer.First stratiform phosphenylic acid zirconium and sulfonation benzenephosphonic acid zirconium and catalyzed reaction thereof have been carried out systematic study, first synthesis characterization solid alkali, solid alkali and the solid super base of quaternary ammonium salt catalyzer, phosphonic acids barium salt and zirconates load of sulfonation toluene phosphonic acids zirconium, alpha-phosphate hydrogen zirconium and organic and inorganic mixed phosphate zirconium-iron(ic) chloride mixture, zirconium phosphate load; Organic side chain has the organic and inorganic mixed phosphate Zr catalyst carrier and the corresponding transition-metal catalyst thereof of coordinating groups such as O, N, P, has studied these their catalytic performances.Though in the research we find these organic and inorganic mixed phosphates as functional materials have synthetic method simple, at active higher, Heat stability is good under the polarizable medium condition, advantage such as can under higher temperature of reaction, use, but it is too obviously outstanding also to exist performance on the high side, inorganics, under hydrophobic conditions activity lower, be difficult to further carry out chemical reaction or modification, the limitation that lacks organic macromolecule toughness etc. self is preferably carried out compound, modification or is carried out chemically modified with the organic functional material precursor.
Composite technology, especially composite organic-inorganic material technology have been opened up brand-new field for the research of exploring novel material.Organic and inorganic material by compound can be when keeping each composition material primary characteristic, produce the not available new capability of independent organic or inorganic material, therefore research and exploration novel organic-inorganic matrix material are subjected to scientific worker's extensive attention day by day.
If can be with volume recombination before organic and inorganic mixed phosphate and the organic functions macromolecular material, mutually modify, modification mutually, turn to one, learn from other's strong points to offset one's weaknesses mutually, realize " combination among the strong ones ", have complementary advantages, constitute novel organic-inorganic complex function macromolecular material precursor, the functional high molecule material that is set out and synthesized by these novel precursors will have particular performances and brand-new purposes so.
Based on such consideration imagination, organic functions macromolecular material precursor compound of organic and inorganic mixed phosphate and polystyrene or this quasi-representative at first explored by the inventor's seminar.We were raw material with ortho phosphorous acid and vinylbenzene in 20 02 years, adopted free radical reaction to synthesize low polystyrene base phosphonous acid first, had studied influence (Fu Xiang-Kai, the Sui Yan of different initiators to reaction mechanism; Chinese Chemical Letters (Chinese chemical wall bulletin); 2002,13 (3): 219-222).Our reported first successfully was oxidized to low polystyrene base phosphonous acid low polystyrene base phosphonic acids (Fu Xiangkai, Sui Yan in 2004; Southwestern Normal University's journal (certainly), 2004,29 (4): 642-646).Thereafter, our reported first successfully synthesizes organic and inorganic mixed phosphate and polystyrene compound novel organic-inorganic composite functional material, the sulfonation low polystyrene base phosphonic acids-phosphoric acid hydrogen zirconium of zirconium white load and the sulfonation low polystyrene base phosphonic acids-novel ion-exchanger of phosphoric acid hydrogen zirconium and the solid acid of titanium dichloride load.So far, the compound initial success that obtained of organic and inorganic mixed phosphate and polystyrene.
For low polystyrene base phosphonic acids-phosphoric acid hydrogen zirconium is further carried out modification and chemically modified, we carry out chloromethylation (Fu Xiangkai, Sui Yan, Fu Dan, Fu Hong with the phenyl ring of low polystyrene base phosphonic acid-phosphate; The Chinese invention patent application: monochloromethyl-ether synthesizes chloromethylation oligopolystyrene phosphonic acid-phosphate; Application number: 200510057167.2), the chloromethyl on the importing low polystyrene base phosphonic acid-phosphate phenyl ring can further react with organic amine, amino acid, organic phosphine, organic arsine, alcohols, phenolic compound, heterogeneous ring compound, mercaptan, phenyl-sulfhydrate compounds, prussiate, cyanate or thiocyanate-compounds and change other useful functional group into; Also can be converted into aldehyde or function perssad carboxylate or the like through reactions such as hydrolysis, oxidations.Thereby can develop a series of is the organic and inorganic complex function polymer of carrier with low polystyrene base phosphonic acid-phosphate.Synthesized low polystyrene base phosphonic acid-phosphate with regard to low polystyrene base phosphonic acid-phosphate with polyamines, multiethylene-glycol reaction such as us and propped up polyamines, the multiethylene-glycol Mo title complex epoxidation catalysts of carrying with chloromethylation.
The linear low polystyrene base of aforesaid method synthetic phosphonic molecule, its polymerization degree is no more than 100 usually, and just is connected with a phosphonyl group at the polystyrene end of the chain.When synthetic linear low polystyrene base phosphonous acid, because the chain termination reaction and the chain transfer reaction of free radical reaction, may cause the linear low polystyrene base phosphonous acid molecule of only a few respectively to be connected with a phosphonous acid group at the head and the tail two ends, so just might connect two phosphonous acid groups in this molecule, will be on the head and the tail two ends connect after the oxidation two phosphonyl groups.But like this molecule of the linear oligomeric stupid vinyl phosphonate that obtains, its phosphonic position neither can be in the middle of the polystyrene carbochains, also can be on benzene ring of polystyrene.
On the other hand, phosphine acidifying polystyrene itself is exactly a kind of ion-exchange material and resin, and the position that phosphonyl group connects can also can be on carbochain on the polystyrene phenyl ring.Connect the polystyrene of phosphonyl group on the phenyl ring usually by PCl
3At AlCl
3Catalysis reacts on phenyl ring with polystyrene down that hydrolysis again prepares.And the polystyrene of connection phosphonyl group on the carbochain, except the above-mentioned linear low polystyrene base phosphonic acids and salt thereof that connects phosphonyl group at the polystyrene end of the chain, connect the polystyrene of phosphonyl group in the middle of the carbochain, do not see bibliographical information so far as yet, also do not have patent application.And the linear low polystyrene base of aforesaid method synthetic phosphonic acids molecular weight is less, and its polymerization degree is usually less than 100, and further the organic and inorganic complex function polymer of reaction making may can not show significant polymer effect.In addition, low polystyrene base phosphonous acid need just can obtain low polystyrene base phosphonic acids through nitric acid oxidation, and in this process, the generation of the degree of oxidation, the introducing of impurity and side reaction all can influence the high molecular performance of final organic and inorganic complex function.
If with the phosphonic acids that has olefin group (C=C) directly and vinylbenzene carry out copolyreaction, will a step obtain vinylbenzene and phosphonic block or alternating copolymer, just phosphonyl group can be connected to the carbochain middle part of polystyrene copolymer, also avoided the oxidising process of phosphonous acid, helped simplifying step, improve productive rate and multipolymer purity.
Summary of the invention
The objective of the invention is to have the isopropylene phosphonic acid of unsaturated double-bond and styrene copolymerized, directly a plurality of one steps of phosphonyl group are introduced in the polystyrene segment, obtain vinylbenzene and phosphonic block or alternating copolymer, can control phosphonic content in the multipolymer easily by changing polymerizing condition.Change styrene-isopropylene phosphonic acid copolymer the organic and inorganic composite phosphate of corresponding poly-(styrene-isopropylene phosphonic acid) salt or poly-(styrene-isopropylene phosphonic acid) into, just can realize organic functions macromolecular material precursor compound of organic and inorganic mixed phosphate and this quasi-representative of polystyrene.And then the synthetic NEW TYPE OF COMPOSITE functional high molecule material of exploitation with special performance and brand-new purposes.
Styrene-isopropylene phosphonic acid copolymer is crossed following processing method and is obtained:
A certain amount of isopropylene phosphonic acid and initiator dibenzoyl peroxide or Diisopropyl azodicarboxylate are dissolved in the solvent, heating, 60～90 ℃, stir under drip styrene, reaction 6～16h; Steam solvent, be washed with distilled water to neutrality again, tell water; Obtain gelatinoid, the oven dry get final product the styrene-isopropylene phosphonic acid copolymer product;
Wherein the vinylbenzene in the reaction and the mol ratio of isopropylene phosphonic acid are 0.25～4.0: 1;
The consumption of initiator dibenzoyl peroxide or Diisopropyl azodicarboxylate is 0.02～0.3: 1 with monomer isopropylene phosphonic acid and cinnamic quality summation ratio.
Free radical solution polymerization is adopted in the copolyreaction of vinylbenzene and polar unsaturated compounds usually.The solvent that adopts is the mixed solvent of lower alcohols such as toluene, tetrahydrofuran (THF), ethyl acetate, ethanol and these organic solvents and water normally.Usually the radical initiator that adopts is dibenzoyl peroxide or Diisopropyl azodicarboxylate.
The distribution of isopropylene phosphonic acid monomer and styrene monomer is segmented copolymer or alternating copolymer in principle in the styrene-isopropylene phosphonic acid copolymer molecule.But because cinnamic reactivity ratio is much larger than isopropylene phosphonic acid, therefore in fact the distribution of isopropylene phosphonic acid monomer and styrene monomer presents the distribution of the similar statistic copolymer of BBBABBBBBBABBBBBBBBBBBABBBB......, in other words in the styrene-isopropylene phosphonic acid copolymer molecule between the polystyrene segment of the irregularly single embedding different quantities of isopropylene phosphonic acid, the structure that seldom or does not almost have two isopropylene phosphonic acid monomers directly to link to each other.Can represent with following formula:
In the formula, R1 is methyl CH
3M is the mean number of styrene monomer between two isopropylene phosphonic acid chain links in the copolymer molecule, n is the monomeric mean number of isopropylene phosphonic acid in the copolymer molecule, and m is 3～30 according to this patent synthetic styrene-isopropylene phosphonic acid copolymer, and n is 2～20.The phosphonic acids cubage of the aqueous sodium hydroxide solution titration multipolymer of n value available standards concentration obtains.Because styrene-isopropylene phosphonic acid copolymer does not also have the viscosity-average molecular weight calculating formula, the m value calculates with multipolymer viscosity with reference to the viscosity-average molecular weight calculating formula of vinylbenzene autopolymer only, the multipolymer that obtains so also viscosity-average molecular weight and m value obviously has a certain distance with actual molecular weight and m value, and is only for referencial use at present.(originally m, n are wrong, correct)
Styrene-isopropylene phosphonic acid copolymer both can be the polymerization degree lower (as the polymerization degree below 100) thus the also lower oligomeric copolymer of molecular weight, can be again the polymerization degree medium and higher (hundreds of, thousands of) as the polymerization degree thus the also higher high polyarylene block copolymer of molecular weight.
During the present invention was raw materials used, isopropylene phosphonic acid was by acetone, phosphorus trichloride and acetic acid reference literature (Zhao Yansheng, Li Wanjie etc.; Synthetic and the sign of isopropylene and phosphonic acid, TaiYuan Industry University's journal, 1996,27 (2): 11～16) Bao Dao preparation method is synthetic, and the isopropylene phosphonic acid of preliminary purification is a light yellow viscous liquid, characterizes its structure through infrared spectra and nuclear magnetic resonance spectrum.Isopropylene phosphonic acid content according to this method preparation is about 95%, is used further to synthesizing styrene-isopropylene phosphonic acid copolymer after can further purifying, but the comparatively loaded down with trivial details complexity of method of purification, and effect is not ideal; Also can be directly used in patent synthesizing styrene-isopropylene phosphonic acid copolymer of the present invention, and need not be further purified, wherein the impurity of 5% left and right sides content mainly is inorganic phosphate, phosphorous acid, and their existence does not influence isopropylene phosphonic acid and cinnamic copolyreaction.
Adopt styrene-isopropylene phosphonic acid copolymer of the present invention that following several characteristics is arranged:
(1), only directly phosphonyl group is introduced in the polystyrene copolymer segment, and the past is by AlCl with single step reaction
3Catalysis PCl
3On phenyl ring, introduce phosphonyl group, and the synthetic two-step reaction at least that all needs of low polystyrene base phosphonic.
(2), contain a plurality of phosphonyl groups in the styrene-isopropylene phosphonic acid copolymer molecule, only contain one unlike majority in the low polystyrene base phosphonic molecule, minority only contains two phosphonyl groups.
(3), styrene-isopropylene phosphonic acid copolymer can be controlled easily and changes phosphonic content in the multipolymer, thereby also can control and change the hydrophilic-hydrophobic of multipolymer easily by changing the copolymerization proportion of raw materials.Less for molecular weight higher (hundreds of, thousands of) and phosphonic acids content (as vinylbenzene: styrene-isopropylene phosphonic acid copolymer isopropylene phosphonic acid＞15) as the polymerization degree, show obvious hydrophobic, be soluble in the not high organic solvent of toluene, this class polarity of chloroform.Higher for molecular weight medium or lower (as the polymerization degree hundreds of even 100 following), phosphonic acids content (as vinylbenzene: the styrene-isopropylene phosphonic acid copolymer of isopropylene phosphonic acid＜8, will show certain wetting ability, be soluble in tetrahydrofuran (THF), this class hydrophilic organic solvent of ethanol.
(4), styrene-isopropylene phosphonic acid copolymer can also further prepare organic and inorganic phosphoric acid mixing salt.The organic and inorganic phosphoric acid mixing salt of preparation the metal ion of organic-inorganic performance, hydrophilic-hydrophobic etc. and mixed phosphate be closely related.As: an alkali metal salt of multipolymer mixed phosphate can show the wetting ability stronger than stupid ethene-isopropylene phosphonic acid copolymer, causes the decreased solubility in organic solvent simultaneously; The solvabilities of tetravalent metal salt in water and in the organic solvent such as the titanium of multipolymer mixed phosphate, zirconium, cerium, tin, lead are all very low, and have laminate structure and certain specific surface, thereby can be used as novel inorganic-organic composite catalyzing agent carrier.Divalence, the trivalent metal salt solvabilities in water and in the organic solvent such as the calcium of multipolymer mixed phosphate, magnesium, barium, iron, manganese, copper, zinc, cadmium, mercury, aluminium, gallium, rare earth are lower than styrene-isopropylene phosphonic acid copolymer usually, but may have different constitutional featuress and purposes.
The styrene-isopropylene phosphonic acid copolymer of the present invention's preparation can be used as the product of a kind of novel organic-inorganic composite functional material precursor or intermediate and sells, and also can carry out the novel organic-inorganic complex function polymer that modification and chemically modified further prepare different structure feature and purposes on the phenyl ring of its polystyrene segment.
Embodiment
Embodiment one:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, use the 150ml dissolve with ethanol, add 2.08g (account for two kinds of comonomer quality and 6.3%) initiator B PO, stir and drip 0.2mol vinylbenzene down, be warming up to about 80 ℃, back flow reaction 9 hours gets the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain white solid.After measured, the m value is about 18 in the multipolymer, and the n value is about 13.5.
Embodiment two:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, use the 150ml acetic acid ethyl dissolution, add 2.08g (account for two kinds of comonomer quality and 6.3%) initiator B PO, stirring down, dropping 0.2mol vinylbenzene is warming up to about 80 ℃, back flow reaction 10 hours gets the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain faint yellow solid.After measured, the m value is about 12 in the multipolymer, and the n value is about 21.3.
Embodiment three:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, dissolve with the 150ml tetrahydrofuran (THF), add 2.08g (account for two kinds of comonomer quality and 6.3%) initiator B PO, stir and drip 0.2mol vinylbenzene down, be warming up to 65～70 ℃, back flow reaction 8 hours gets the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain faint yellow solid.After measured, the m value is about 9.1 in the multipolymer, and the n value is about 29.8.
Embodiment four:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, dissolve with the 150ml tetrahydrofuran (THF), add 2.08g (account for two kinds of comonomer quality and 6.3%) initiator Diisopropyl azodicarboxylate ABIN, stir and drip the stupid ethene of 0.2mol down, be warming up to 65～70 ℃, reacted 9 hours, get the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain faint yellow solid.After measured, the m value is about 10.2 in the multipolymer, and the n value is about 16.4.
Embodiment five:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.15mol isopropylene phosphonic acid, use the 200ml dissolve with ethanol, add 3.12g (account for two kinds of comonomer quality and 8.6%) initiator B PO, stir and drip 0.2mol vinylbenzene down, be warming up to about 80 ℃, back flow reaction 11 hours gets the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain white solid.After measured, the m value is about 13.4 in the multipolymer, and the n value is about 12.1.
Embodiment six:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.15mol isopropylene phosphonic acid, use the 200ml acetic acid ethyl dissolution, add 3.12g (account for two kinds of comonomer quality and 8.6%) initiator B PO, stir and drip 0.2mol vinylbenzene down, be warming up to about 80 ℃, back flow reaction 11.5 hours gets the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain faint yellow solid.After measured, the m value is about 8.4 in the multipolymer, and the n value is about 20.5.
Embodiment seven:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.15mol isopropylene phosphonic acid, dissolve with the 150ml tetrahydrofuran (THF), add 3.12g (account for two kinds of comonomer quality and 8.6%) initiator B PO, stir and drip 0.2mol vinylbenzene down, be warming up to about 65～70 ℃, back flow reaction 15 hours gets the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain faint yellow solid.After measured, the m value is about 7.4 in the multipolymer, and the n value is about 22.3.
Embodiment eight:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, dissolve with the 150ml tetrahydrofuran (THF), the initiator B PO that adds different amounts, stir and drip 0.2mol vinylbenzene down, be warming up to 65～70 ℃, back flow reaction 8～10 hours gets the styrene-isopropylene phosphonic acid copolymer jelly.Steam solvent, washing, the dry styrene-isopropylene phosphonic acid copolymer that gets.The n value that the m value that phosphonic acids content is relevant in the multipolymer is relevant with the multipolymer viscosity-average molecular weight increases with initiator amount and changes as following table:
Embodiment nine:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, the isopropylene phosphonic acid that adds different amounts, with the dissolving of 150ml tetrahydrofuran (THF), add 2.3g initiator B PO, stir and drip 0.1mol vinylbenzene down, be warming up to 65～70 ℃, reacted 12 hours, and got copolymer solution, steam solvent, washing, the dry styrene-isopropylene phosphonic acid copolymer that gets.The m value that phosphonic acids content is relevant in the multipolymer n value relevant with the multipolymer viscosity-average molecular weight is with the variation such as the following table of isopropylene phosphonic acid consumption:
Embodiment ten:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, with the dissolving of 200ml tetrahydrofuran (THF), add 2.3g initiator B PO, stir and drip 0.3mol vinylbenzene down, be warming up to 65～70 ℃, reacted 9 hours, and got copolymer solution, steam solvent, washing, the dry styrene-isopropylene phosphonic acid copolymer that gets.After measured, the m value is about 10.7 in the multipolymer, and the n value is about 30.6.
Embodiment 11:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, dissolve with the 150ml n-propyl alcohol, add 2.08g (account for two kinds of comonomer quality and 6.3%) initiator B PO, stir and drip 0.2mol vinylbenzene down, be warming up to about 90 ℃, reacted 9 hours, get the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain white solid.After measured, the m value is about 14.2 in the multipolymer, and the n value is about 17.4.
Embodiment 12:
In the 250ml there-necked flask of agitator, reflux exchanger and thermometer is housed, add the 0.1mol isopropylene phosphonic acid, dissolve with the 150ml Virahol, add 2.08g (account for two kinds of comonomer quality and 6.3%) initiator B PO, stir and drip 0.2mol vinylbenzene down, be warming up to about 80 ℃, reacted 9 hours, get the styrene-isopropylene phosphonic acid copolymer jelly.Washing, drying obtain white solid.After measured, the m value is about 13.3 in the multipolymer, and the n value is about 16.5.
Claims (2)
1. styrene-isopropylene phosphonic acid copolymer is characterized in that this multipolymer obtains by following processing method:
Isopropylene phosphonic acid and initiator dibenzoyl peroxide or Diisopropyl azodicarboxylate are dissolved in the solvent, heating, 60～90 ℃, stir under drip styrene, reaction 6～16h; Steam solvent, be washed with distilled water to neutrality again, tell water; Obtain gelatinoid, the oven dry get final product the styrene-isopropylene phosphonic acid copolymer product;
The mol ratio of vinylbenzene and isopropylene phosphonic acid is 0.25～4.0: 1 in the reaction;
The consumption of initiator dibenzoyl peroxide or Diisopropyl azodicarboxylate is 0.02～0.3: 1 with monomer isopropylene phosphonic acid and cinnamic quality summation ratio;
Contain the phosphonyl group of a plurality of P-C of having keys in the described styrene-isopropylene phosphonic acid copolymer molecule, structural formula is as follows:
In the formula, R
1Be methyl CH
3, m is the mean number of styrene monomer between two isopropylene phosphonic acid chain links in the copolymer molecule, and n is the monomeric mean number of isopropylene phosphonic acid in the copolymer molecule, and m is 3～30, and n is 2～20.
2. styrene-isopropylene phosphonic acid copolymer according to claim 1, it is characterized in that described solvent is toluene, tetrahydrofuran (THF), ethyl acetate or ethanol, their usage quantity is vinylbenzene and two kinds of monomer cumulative volumes of isopropylene phosphonic acid 2.0～8.0 times according to volume.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446028A (en) * | 1982-12-20 | 1984-05-01 | Betz Laboratories, Inc. | Isopropenyl phosphonic acid copolymers used to inhibit scale formation |
| US5109033A (en) * | 1991-05-16 | 1992-04-28 | Arco Chemical Technology, L.P. | Vinyl aromatic monomer/vinyl phosphonate copolymer compositions and foamed articles derived therefrom |
| US5594084A (en) * | 1994-12-07 | 1997-01-14 | Betzdearborn Inc. | Alkyl-allylphosphonate copolymer used for boiler water treatment |
| CN1309148A (en) * | 2000-02-16 | 2001-08-22 | 北京燕山石油化工公司研究院 | Copolymer of isopropylene and phosphonic acid and its use |
| US20060009654A1 (en) * | 2004-07-07 | 2006-01-12 | Dabdoub Atif M | Methods for synthesizing phosphonic compounds and compounds thereof |
-
2006
- 2006-08-22 CN CNB2006100950531A patent/CN100448900C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446028A (en) * | 1982-12-20 | 1984-05-01 | Betz Laboratories, Inc. | Isopropenyl phosphonic acid copolymers used to inhibit scale formation |
| US5109033A (en) * | 1991-05-16 | 1992-04-28 | Arco Chemical Technology, L.P. | Vinyl aromatic monomer/vinyl phosphonate copolymer compositions and foamed articles derived therefrom |
| US5594084A (en) * | 1994-12-07 | 1997-01-14 | Betzdearborn Inc. | Alkyl-allylphosphonate copolymer used for boiler water treatment |
| CN1309148A (en) * | 2000-02-16 | 2001-08-22 | 北京燕山石油化工公司研究院 | Copolymer of isopropylene and phosphonic acid and its use |
| US20060009654A1 (en) * | 2004-07-07 | 2006-01-12 | Dabdoub Atif M | Methods for synthesizing phosphonic compounds and compounds thereof |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and Characterization of Poly (styrene-co-vinylphosphonate) Ionomers. QI WU, R.A. WEISS.Journal of Polymer science: Part B: Polymer Physics,Vol.42 . 2004 |
| Synthesis and Characterization of Poly (styrene-co-vinylphosphonate) Ionomers. QI WU, R.A. WEISS.Journal of Polymer science: Part B: Polymer Physics,Vol.42 . 2004 * |
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