CN100503476C - Preparation method for highly effective maleic anhydride series polymer antisludging agent - Google Patents
Preparation method for highly effective maleic anhydride series polymer antisludging agent Download PDFInfo
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- CN100503476C CN100503476C CNB2007100516797A CN200710051679A CN100503476C CN 100503476 C CN100503476 C CN 100503476C CN B2007100516797 A CNB2007100516797 A CN B2007100516797A CN 200710051679 A CN200710051679 A CN 200710051679A CN 100503476 C CN100503476 C CN 100503476C
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Abstract
The invention discloses a preparing method of effective maleic anhydride system polymeric compound antisludging agent belonging to chemical industry technical and water disposal domain, which comprises the following steps: adding overdraw multi-double bond monomer in the maleic anhydride series antisludging agent synthetic course; proceeding polymerization; increasing molecular weight and combination property of maleic anhydride homopolymer. This invention can be applied to recycle cooling water system, boiler water, oil field water, paper making and seawater desalinization.
Description
Technical field
The present invention relates to the preparation method of highly effective maleic anhydride series polymer antisludging agent.This Scale inhibitors is as the dispersing and antisludging agent of water quality.
Background technology
The field that relates to water treatment comprises: industrial circulating cooling water, oiler feed, papermaking, petroleum industry, sea water desalinization etc.Fouling may bring serious consequence to production, reduces throughput, even causes shut-down.In industrial circulating cooling water system, CaCO
3Be the most common dirt, usually cause the fouling of equipment pipe internal surface, influence flowing and heat transfer efficiency of water, serious caused line clogging causes shut-down.In paper industry, CaCO
3, BaSO
4Be pulp digester, give birth to common dirt in liquid (undressed stoste) pipeline, bleaching system and the extraction element, the formation of these dirts increases consumption, the reduction of steam and gives birth to liquid ducted mobile, increases the saltcake loss, and then reduction quality product and throughput.In petroleum industry, CaCO
3, CaSO
4, BaSO
4Be the main component of dirt, can cause the decline of throughput.In the saturating desalination of seawater reverse osmosis, CaSO
4, BaSO
4, SrSO
4Be the main component of dirt, these dirts can stop up film, cause that membrane flux reduces, and throughput descends, and membrane lifetime shortens, and increases production cost, and serious also can causing produced and stopped work.Therefore the processing of the scale inhibition of service water is the research topic that people paid close attention to always.Scale inhibitors is a kind of ether-containing key, carboxyl, amido, sulfonic group, the polymkeric substance of phosphino-, hydroxyl etc., multiple fouling had certain scale inhibition and dispersive ability, and have certain corrosion inhibition, utilize to add Scale inhibitors to carry out that scale inhibition handles be convenient relatively and a kind of method efficiently in numerous method of scale inhibition.
At present, in numerous Scale inhibitorss, maleic anhydride series Scale inhibitors demand is still very big, because without phosphorus, is considered to nontoxic, pollutes very little, environmentally acceptable water treatment agent, this family macromolecule Scale inhibitors, much suitability for industrialized production.But general molecular weight is not high.Because the symmetrical structure that maleic anhydride is special, make its polymerization difficulty, a kind of method that improves its molecular weight at present is to seek new catalyzer, change the structure-activity of maleic anhydride, new screening of catalyst will be done a large amount of work, need the testing installation condition, the manpower of input, material resources are all very big; Another kind method is to add the polymerization that one or more monomers drive maleic anhydride, as vinylformic acid, methacrylic acid, methyl acrylate, vinyl-acetic ester, methacrylic ester, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, acrylamide, Methacrylamide, propene sulfonic acid, methacrylic sulfonic acid, sodium allylsulfonate, methylpropene sodium sulfonate, vinyl acetate, 2-first propyl sulfonic acid, 2-first propyl sulfonic acid sodium, styrene sulfonic acid, Sodium styrene sulfonate, monomers such as maleic sulfonic acid dicarboxylic acid, add above-mentioned monomer and improve the transformation efficiency of maleic anhydride on the one hand, improve other performance on the other hand by the monomer that adds.This respect has a lot of research, but the monomer effect of single, double functional group is not fine, and over-all properties, effect are remarkable inadequately.The increase that this has just caused consumption has increased cost.
Hyperbranched polymer has closely like globosity, the periphery has a large amount of end groups, after these end groups carry out necessary modification, can obtain unique function, the present invention passes through the terminal-modified of a step or multistep with hyperbranched polymer (hyper-branched polyester, hyperbranched polyether, hyperbranched poly esteramides), obtaining the monomer that end contains many pairs of keys is hyperbranched many double bond monomers, adds the molecular weight that hyperbranched many double bond monomers improve polymkeric substance in maleic anhydride series polymer.Because this hyperbranched many double bond monomers contain branched structure, cause its solvability height than linear homologue, the additive as water conditioner preferably, fine really from the effect of using, and do not appear in the newspapers on the domestic and foreign literature and lead.
Summary of the invention
The objective of the invention is to seek the method that a kind of effective way improves the maleic anhydride series polymer antisludging agent molecular weight, improve its over-all properties and scale inhibition effect with this.This method can directly be used under the synthetic optimal conditions of original maleic anhydride series Scale inhibitors, and method is fast and convenient.
The preparation method of a kind of highly effective maleic anhydride series polymer antisludging agent of the present invention, containing double bond monomer with maleic anhydride and one or more is raw material, be made into the aqueous solution or organic solution, in the presence of catalyzer or oxygenant or oxidation-reduction agent, carry out radical polymerization at-5 ℃～200 ℃, in polymerization process, add hyperbranched many double bond monomers: obtain the macromolecule maleic anhydride series polymer antisludging agent.
Preparation method's step of highly effective maleic anhydride series polymer antisludging agent of the present invention is:
1), in reaction vessel (thermometer, agitator and reflux condensate device are housed), adds solvent, maleic anhydride, transition metal ion catalyzer and hydroquinone of polymerization retarder, the molar ratio that they add is 2:1:0.005:0.005, stir into homogeneous solution, described solvent is organic solvent such as toluene, Virahol etc., the mixture of perhaps water, or organic solvent and water;
2), in the solution that step 1) obtains, drip one or more double bond containing monomers, add-on is that every gram maleic anhydride adds 0.5～075 milliliter, drip hyperbranched many double bond monomers simultaneously, add-on is 0.05～0.15 times of maleic anhydride quality, stirring reaction 0.5～40 hour, temperature of reaction are controlled at-5 ℃～200 ℃;
3) if what use in the step 1) is organic solvent, then with step 2) reactor product come out with precipitation agent acetone, ether, tetrahydrofuran (THF) or their mixture washing precipitation, add the entry wiring solution-forming then, be Scale inhibitors; If water is a solvent in the step 1), then product is directly made Scale inhibitors, or adds the concentration that entry is made into use, is Scale inhibitors;
Wherein, described maleic anhydride series polymer comprises maleic anhydride homopolymer and its multipolymer; The described double bond monomer that contains is basic sulfonic acid, 2-first propyl sulfonic acid sodium, styrene sulfonic acid, Sodium styrene sulfonate or a maleic sulfonic acid dicarboxylic acid in vinylformic acid, methacrylic acid, methyl acrylate, vinyl-acetic ester, methacrylic ester, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, acrylamide, Methacrylamide, propene sulfonic acid, methacrylic sulfonic acid, sodium allylsulfonate, methylpropene sodium sulfonate, vinyl acetate, the 2-first; Described catalyzer is the transition metal ion catalyzer---ferrous sulfate or alchlor; Described oxygenant is Sodium Persulfate, ammonium persulphate, hydrogen peroxide, benzoyl peroxide or Diisopropyl azodicarboxylate; Described reductive agent is cupric salt, molysite, Sodium Pyrosulfite, Sulfothiorine or hydrosulphite;
Described hyperbranched many double bond monomers are hyperbranched polymers that end contains many pairs of keys, by the hyper-branched polyester, hyperbranched polyether or the super-branched polyesteramide that contain great amount of hydroxy group end functional group by a step or multistep is terminal-modified obtains.
Described hyper-branched polyester is made by polymerization progressively by acid anhydrides or acid and dibasic alcohol, the preparation method is: add acid anhydrides or acid, solvent and catalyzer in reaction vessel (agitator, reflux exchanger, thermometer, constant pressure funnel are housed), solvent adding amount is acid anhydrides or sour quality 2 times, catalytic amount is 0.001 of acid anhydrides or a sour quality, stir, dripping dibasic alcohol under agitation condition reacts, temperature of reaction is controlled at-10 ℃～250 ℃, preferred 0 ℃～200 ℃, reaction times is 0.5～30 hour, preferred 0.5～25 hour.Reaction precipitates product after finishing with precipitation agent, throw out promptly obtains hyper-branched polyester 45 ℃～250 ℃ dryings, wherein said acid anhydrides is a trimellitic acid 1,2-anhydride, and acid is dihydroxyalkyl propionic acid etc., and described dibasic alcohol is 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol or Diethylene Glycol.
The hyper-branched polyester that contains terminal hydroxy group is by A
2And B
3Monomer is synthetic, at first A
2And B
3In B reaction generate AB
2Monomer further generates hyper-branched polyester, A from polycondensation then
2Monomer is a Succinic anhydried, Pyroglutaric acid, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride or substituent cyclic acid anhydride, B are arranged
3Monomer comprises TriMethylolPropane(TMP), glycerine, R-GLYCIDOL, glycerol, AB
2Monomer comprises the monomer that contains two hydroxyls of a carboxyl.
Described hyperbranched polyether is by Racemic glycidol and TriMethylolPropane(TMP), perhaps glycidyl ether and TriMethylolPropane(TMP), perhaps glycidyl ether and 3-ethyl-3-methylol butylene oxide ring, perhaps glycidyl ether and 3-methyl-3-methylol butylene oxide ring, polycondensation or ring-opening polymerization form, method be reaction vessel (agitator is housed, thermometer, constant pressure funnel) lining, add solvent and oxy-compound, solvent adding amount is 2 times of oxy-compound amount, logical nitrogen, it is identical with the oxy-compound amount to drip Racemic glycidol or its amount of glycidyl ether, temperature of reaction is controlled at-10 ℃～250 ℃, preferred 0 ℃～200 ℃, reaction times is 0.5～30 hour, preferred 0.5～25 hour, after reaction finishes, product precipitates with precipitation agent, and throw out promptly obtains hyperbranched polyether 25 ℃～70 ℃ dryings, wherein, described polynary azanol comprises Tutofusin tris, diethanolamine, diisopropanolamine (DIPA); Described acid anhydrides comprises Succinic anhydried, Pyroglutaric acid, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, substituent cyclic acid anhydride is arranged.
Described hyperbranched poly esteramides is made by step-reaction polymerization by polynary azanol and acid anhydrides, method is (thermometer to be housed at reaction vessel, agitator, reflux exchanger, constant pressure funnel) adds amine in, solvent and catalyzer, their mol ratio is 1:2:0.005, drip the acid anhydrides of stoichiometric ratio, temperature of reaction is controlled at-10 ℃～250 ℃, reaction times was controlled at 0.5～30 hour, after reaction finishes, product 25 ℃～200 ℃ dryings, promptly obtains the hyperbranched poly esteramides in the aqueous solution of sodium hydroxide and after purifying, wherein, described polynary azanol comprises Tutofusin tris, diethanolamine, diisopropanolamine (DIPA); Described acid anhydrides comprises Succinic anhydried, Pyroglutaric acid, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, substituent cyclic acid anhydride is arranged.
In above-mentioned preparation hyper-branched polyester, hyperbranched polyether, hyperbranched poly esteramides, described solvent is one or more in chloroform, methylene dichloride, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), the dimethyl formamide; Described catalyzer is one or more in hydrochloric acid, Phenylsulfonic acid, toluene sulfonic acide, sulfuric acid, potassium methylate, tetraethylammonium bromide, the boron trifluoride ethyl ether complex; Used precipitation agent is acetone, ether, tetrahydrofuran (THF) or their mixture.
It is to be the compound modified of thiazolinyl with end group directly that described one step of hyperbranched polymer is modified as hyperbranched many double bond monomers, makes end have many pairs of keys.Method is (thermometer to be housed at reaction vessel, agitator, reflux exchanger, constant pressure funnel) in add 10 parts of hyperbranched monomers by mass fraction, 40 parts of solvents, 0.005 part of catalyzer tosic acid, 0.005 part of logical nitrogen of hydroquinone of polymerization retarder drips the monomer reaction that contains thiazolinyl by stoichiometry, temperature of reaction is controlled at-10 ℃～200 ℃, preferred 0 ℃～150 ℃, the reaction times is 0.5～20 hour, preferred 0.5～15 hour.After reaction finishes, add the precipitation agent washing, obtain hyperbranched many double bond monomers 20 ℃～100 ℃ dryings, double bond containing acid, acid anhydrides or the acyl chlorides of used properties-correcting agent for reacting with hydroxyl, as vinylformic acid, methacrylic acid, acrylate chloride; Solvent is toluene, dimethylbenzene etc.
The step that described hyperbranched polymer multistep is modified as hyperbranched many double bond monomers is: it is amido that a step becomes end group with the modification of raw material organism, the intermediate of carboxyl or hydroxyl, its method is according to concrete organic raw material, synthetic method is carried out routinely, when terminal groups modification is amido, select dimethylamine or diethylamine for use, under the condition of pressurization of heating and end group be the organism generation dehydration reaction of hydroxyl, generating end group is the tertiary amine intermediate; Further use the alkenyl monomer modification then, make that terminal group is a thiazolinyl, this goes on foot the vinyl carboxylic acid, chloro thiazolinyl alkane or the compound aromatic base that contain two keys of used properties-correcting agent for reacting with the end group after the first step modification, as vinylformic acid, methacrylic acid, acrylate chloride, p-chloromethyl styrene or glycidyl allyl ether.The modified-reaction temperature is-10 ℃～200 ℃, and the reaction times is 0.5～20 hour; Best temperature of reaction is 0 ℃～150 ℃, and the reaction times is 0.5～15 hour.
Such as the further raw material of modified-reaction is after the first step modification during for the amido end group, select for use p-chloromethyl styrene to carry out the synthetic quaternary amine of quaternary ammonium reaction, hyperbranched quaternary amine is better than the solvability of hyperbranched polymer, so the application different according to hyperbranched monomer selects for use different compounds to carry out modification.
Described copolymer-maleic anhydride contains double bond monomer and carries out radical polymerization and obtain by adding one or more in the maleic anhydride, its method is to add solvent in the reaction vessel that thermometer, agitator, reflux exchanger are housed, maleic anhydride, transition metal ion catalyzer and hydroquinone of polymerization retarder, perhaps drip one or more double bond containing monomers again, temperature of reaction is controlled at-5 ℃～200 ℃; Reaction times was controlled at 0.5 hour～40 hours, after reaction finishes, if what select for use in the process is organic solvent, then the product washing precipitation was come out then to use adding the entry wiring solution-forming; If what select for use in polymerization process is that water is solvent, then can directly use or add the concentration that entry is made into the use needs, the double bond monomer that contains of adding is vinylformic acid, methacrylic acid, methyl acrylate, vinyl-acetic ester, methacrylic ester, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, acrylamide, Methacrylamide, propene sulfonic acid, methacrylic sulfonic acid, sodium allylsulfonate, methylpropene sodium sulfonate, vinyl acetate, 2-first propyl sulfonic acid, 2-first propyl sulfonic acid sodium, styrene sulfonic acid, Sodium styrene sulfonate or maleic sulfonic acid dicarboxylic acid.The transition metal ion catalyzer is ferrous iron, copper, Vanadium Pentoxide in FLAKES, aluminum oxide etc.
The preparation method of described maleic anhydride homopolymer is to add solvent in the reaction vessel that thermometer, agitator, reflux exchanger are housed, maleic anhydride, and transition metal ion catalyzer and hydroquinone of polymerization retarder, temperature of reaction are controlled at-5 ℃～200 ℃; Reaction times was controlled at 0.5 hour～40 hours, after reaction finishes, if what select for use in the process is organic solvent, then the product washing precipitation was come out adding the entry wiring solution-forming then, made Scale inhibitors and used; If what select for use in polymerization process is that water is solvent; then can directly make the concentration that Scale inhibitors uses or add entry to be made into the use needs and make Scale inhibitors; as above-mentioned method; the general solvent that adopts is the organic solvent Virahol; or the aqueous solution; perhaps adopt the mixture of organic solvent and water; with oxygenant or/and the oxidation-reduction agent is the polymerization of radical initiator trigger monomer; wherein oxygenant adopts Sodium Persulfate; ammonium persulphate; hydrogen peroxide; benzoyl peroxide or Diisopropyl azodicarboxylate, reductive agent then adopt cupric salt; molysite; Sodium Pyrosulfite; Sulfothiorine or hydrosulphite.
The present invention adds hyperbranched many double bond monomers and improves its molecular weight in the maleic anhydride based copolymer, hyperbranched many double bond monomers hyper-branched polyester, hyperbranched polyether or hyperbranched poly esteramides made by a step or the terminal-modified of multistep, because this hyperbranched many double bond monomers contain branched structure, cause its solvability height than linear homologue, additive as water conditioner preferably, from the effect of using, fine really.
The scale-inhibiting properties testing method:
Add 250 ml waters in 500 milliliters of volumetric flasks, add the calcium chloride standardized solution with drop-burette, the amount that makes calcium ion is 120 milligrams., add people's water conditioner (maleic anhydride series polymer antisludging agent of the present invention) sample solution with transfer pipet, shake up.Add 20 milliliters of pH=9 borax buffer solution then, shake up with drop-burette and slowly add the sodium bicarbonate standardized solution, the limit edged shakes, and making the amount of bicarbonate ion is 366 milligrams, is diluted with water to scale, shakes up.As test solution.Be equipped with blank test solution with the metering preparation as stated above in addition, blank test solution is not with water conditioner.
Two Erlenmeyer flasks of test solution and blank test solution are immersed in 1 ℃ of 80 scholar's the water bath with thermostatic control (liquid level of test solution must not be higher than the liquid level of water-bath), constant temperature was placed 10 hours.Do filtration with the middling speed quantitative paper after being chilled to room temperature.The filtrate of getting test solution and blank test solution respectively places 250 milliliters of Erlenmeyer flasks respectively for 25.00 milliliters, adds water to about 80 milliliters, adds 5 milliliters of potassium hydroxide solutions and about 0.1 gram calcium-carboxylic acid indicator.Become sapphirine to solution by red-purple with the titration of disodium ethylene diamine tetraacetate (EDTA) standard titration solution and be terminal point.
The scale inhibition performance of Scale inhibitors is calculated as follows
Scale inhibition performance %=(Va-Vo)/(Vb-Vo) * 100%
Va: consume EDTA volume milliliter with water conditioner after the test
Vb: consume EDTA volume milliliter when measuring TC before the experiment
Vo: do not consume EDTA volume milliliter after the test with water conditioner
Embodiment
The synthetic method of this ｀ highly effective maleic anhydride series polymer antisludging agent is described below by example, the preparation of the hyperbranched many double bond monomers that added in the synthesizing efficient maleic anhydride series polymer antisludging agent process, the effect of highly effective maleic anhydride series polymer antisludging agent.
Embodiment 1
Synthesizing of hyper-branched polyester
Take by weighing 0.1 mole 2,2-two (methylol) propionic acid, 4 milligrams of TriMethylolPropane(TMP)s, 0.02 gram toluene sulfonic acide catalyzer moves into thermometer is housed, agitator, in the four-hole boiling flask of reflux condensing tube, 140 ℃ of melt polymerizations 5 hours filter with 500 milliliters of acetone precipitations then, drying is 24 hours under 50 ℃, and it is standby to get white powder hyper-branched polyester solid.
Embodiment 2
Synthesizing of hyper-branched polyester
To spherical condensating tube is housed, constant pressure funnel, add 0.15 mole of dibasic acid anhydride in the three-necked bottle of electronic stirring, make catalyzer and 40 milliliters of 1N with tetraethylammonium bromide, dinethylformamide is warming up to 80 ℃-110 ℃, after being dissolved into homogeneous phase, 0.1 mole of R-GLYCIDOL is slowly dropped in the system, and reaction process is followed the tracks of with acid number, to the constant back discharging of acid number.With water/petroleum ether precipitation separation and purification, 55 ℃-60 ℃ were descended dry 24 hours in vacuum drying oven, and it is standby promptly to get hyper-branched polyester.
Embodiment 3
Synthesizing of hyperbranched polyether
To vacuum-drying, be full of nitrogen and have in two mouthfuls of round-bottomed flasks of stirrer, add 40 milliliters of methylene dichloride and 0.1 mole of 3-ethyl-3-methylol butylene oxide ring, add 0.6 milligram of initiator boron trifluoride ethyl ether complex with microsyringe, polyreaction begins to carry out at 25 ℃.After reaching predetermined reaction times, the dichloromethane solution that is dissolved with phenol is added reaction system with syringe, continue to stir 3 hours.Mixed solution is washed till neutrality with distilled water, and polymkeric substance is sedimentation and filtration in excessive sherwood oil, and gained hyperbranched polyether sample is standby at 40 ℃ times dry 24 hours.
Embodiment 4
Synthesizing of hyperbranched polyether
Add whipping appts and two constant pressure funnels on the three-necked flask, and on two constant pressure funnels, connect nitrogen and liquid seal device respectively.Behind the naked light barbecue apparatus; add 30 milliliters of chloroform solvents and 0.1 mole of glycerol in flask, ice-water bath stirs after 20 minutes down, drips 0.1 mole of Racemic glycidol and boron trifluoride ethyl ether complex under nitrogen protection simultaneously; at room temperature continue after dropwising to stir termination reaction 3 hours.Product in alkali and after, purify with methyl alcohol-ether combination solvent method.In 70 ℃ of vacuum drying ovens dry 24 hours standby.
Embodiment 5
Synthesizing of hyperbranched poly esteramides
Take by weighing 0.1 mole of Tutofusin tris and place the there-necked flask that electronic stirring and drying installation are housed, under the ice-water bath condition, add 15 milliliters of anhydrous methanols, reacted 2 hours, desolventize, add 2 milligrams of tosic acid, 150 ℃ were reacted 5 hours down, and product is through water washing, sedimentation, drying is 24 hours under 50 ℃, and it is standby promptly to get the polyesteramide solid.
Embodiment 6
Synthesizing of hyperbranched poly esteramides
Take by weighing 0.15 mole of diethanolamine, after the chloroform dissolving, move into and be equipped with in the four-hole boiling flask of agitator, thermometer, water trap, reflux dewatering 1 hour, add 0.1 mole of hexahydrophthalic anhydride reaction 3 hours, desolventize, add 5 gram tetramethylolmethanes, 30 milliliters of dimethylbenzene, be warming up to 130 ℃, reacted 6 hours, product is through water washing, sedimentation, drying is 24 hours under 50 ℃, and it is standby promptly to get hyperbranched poly esteramides solid.
Embodiment 7
Hyperbranched many double bond monomers 1
The hyper-branched polyester of above-mentioned preparation is taken by weighing 20 grams, after the toluene dissolving, immigration is equipped with in the four-hole boiling flask of agitator, thermometer, adds 0.5 milligram of Resorcinol, 0.8 milligram of tosic acid, temperature is raised to 100 ℃, add 15 milliliters in vinylformic acid, react after 5 hours the aqueous solution alkali cleaning of sodium hydroxide, drying at room temperature 24 hours, it is standby promptly to obtain hyperbranched many double bond monomers 1.
Embodiment 8
Hyperbranched many double bond monomers 2
The hyperbranched polyether of above-mentioned preparation is taken by weighing 20 grams, dimethylamine 6 grams, 1 milligram of aluminium sesquioxide, move into reactor, under two normal atmosphere, 200 ℃ were reacted 5 hours, product is dissolved in 150 milliliters the acetonitrile, immigration is equipped with in the four-hole boiling flask of agitator, thermometer, adds 0.5 milligram of Resorcinol stopper, and 60 ℃ add 12 gram vinyl Bian Ji chlorine down, treat after 2 hours to be warming up to 70 ℃ after the solution muddiness, reacted 1.5 hours, and be cooled to 40 ℃ of stirrings then and spend the night and desolventize, it is standby that vacuum-drying promptly got hyperbranched many double bond monomers 2 in 24 hours.
Embodiment 9
Hyperbranched many double bond monomers 3
Take by weighing hyperbranched poly esteramides 20 grams of above-mentioned preparation, dimethylamine 5 grams, 1 milligram of aluminium sesquioxide, move into reactor, under two normal atmosphere, 210 ℃ were reacted 8 hours, product is dissolved in 50 milliliters the water, moves into and is equipped with in the four-hole boiling flask of agitator, thermometer, regulates pH=9, add 0.5 milligram of Resorcinol stopper, 40 ℃ add 5.5 gram glycidyl allyl ethers down, and 5 hours postcooling are regulated pH=5 to room temperature, product is washing in a large amount of acetone, and it is standby that vacuum-drying promptly got hyperbranched many double bond monomers 3 in 24 hours.
Embodiment 10
Hyperbranched many double bond monomers 4
The hyperbranched polyether of above-mentioned preparation is taken by weighing 20 grams, after the chloroform dissolving, move into and be equipped with in the four-hole boiling flask of agitator, thermometer, add 0.5 milligram of Resorcinol, 5 milligrams of triethylamines, ice-water bath add down acrylate chloride 10 grams, react that promptly to obtain hyperbranched many double bond monomers 4 after 5 hours standby.
Embodiment 11
The application 1 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide at interval, temperature is controlled at 100 ℃, reacts 3 hours, promptly obtains the high-molecular weight hydrolytic polymaleic anhydride.
Embodiment 12
The application 2 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, the 0.1 hyperbranched many double bond monomers 1 of gram and 10 milliliters of vinylformic acid at interval, temperature is controlled at 95 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 13
The application 3 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, the 0.2 hyperbranched many double bond monomers 4 of gram and 10 milliliters of vinylformic acid at interval, temperature is controlled at 95 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 14
The application 4 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, the 0.3 hyperbranched many double bond monomers 1 of gram and 10 milliliters of vinylformic acid at interval, temperature is controlled at 95 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 15
The application 5 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, 0.1 gram 2,10 milliliters of vinylformic acid of hyperbranched many double bond monomers and 10 milliliters of acrylamides at interval, temperature is controlled at 90 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 16
The application 6 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, 0.2 gram 2,10 milliliters of vinylformic acid of hyperbranched many double bond monomers and 10 milliliters of acrylamides at interval, temperature is controlled at 90 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 17
The application 7 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, 0.3 gram 2,10 milliliters of vinylformic acid of hyperbranched many double bond monomers and 10 milliliters of acrylamides at interval, temperature is controlled at 90 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 18
The application 8 of branched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, 0.1 gram 3,10 milliliters of vinylformic acid of hyperbranched many double bond monomers and 5 milliliters of sodium allylsulfonates at interval, temperature is controlled at 90 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 19:
The application 9 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, 0.2 gram 3,10 milliliters of vinylformic acid of hyperbranched many double bond monomers and 5 milliliters of sodium allylsulfonates at interval, temperature is controlled at 90 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 20
The application 10 of hyperbranched polymer
Take by weighing 20 gram maleic anhydrides, add 20 ml waters, be dissolved in the four-hole boiling flask that agitator, thermometer are housed, drip 20 milliliters of hydrogen peroxide, 0.3 gram 3,10 milliliters of vinylformic acid of hyperbranched many double bond monomers and 5 milliliters of sodium allylsulfonates at interval, temperature is controlled at 90 ℃, reacted 3 hours, and promptly obtained high-molecular weight hydrolysis copolymer-maleic anhydride.
Embodiment 21
The performance of embodiment 11～20 synthetic high-molecular weight hydrolytic polymaleic anhydride and the agent of high-molecular weight hydrolysis maleic anhydride copolymer anti-scale.Test by above-mentioned scale-inhibiting properties testing method, in the sample liquid Scale inhibitors add-on be respectively 1 mg/litre, 2 mg/litre, 3 mg/litre, 4 mg/litre, 5 mg/litre, 6 mg/litre, 7 mg/litre,, 8 mg/litre, 9 mg/litre, 10 mg/litre, as shown in table 1 below.
Table 1 embodiment 11～20 scale-inhibiting properties comparative results
Claims (16)
1. the preparation method of a maleic anhydride series polymer antisludging agent is characterized in that method steps is:
1), in reaction vessel, add 20 ml waters, 20 gram maleic anhydrides drip 20 milliliters of hydrogen peroxide at interval, stir into homogeneous solution;
2), in the solution that step 1) obtains, drip one or more double bond containing monomers, add-on is that every gram maleic anhydride adds 0.5～0.75 milliliter, drip hyperbranched many double bond monomers simultaneously, add-on is 0.005,0.01 or 0.015 times of maleic anhydride quality, stirring reaction 0.5～40 hour, temperature of reaction are controlled at-5 ℃～200 ℃;
3), step 2) product directly make Scale inhibitors, or add the concentration that entry is made into use, be Scale inhibitors;
Wherein, described maleic anhydride series polymer comprises maleic anhydride homopolymer and its multipolymer.
2, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 1, it is characterized in that: described hyperbranched many double bond monomers are hyperbranched polymers that end contains many pairs of keys, by the hyper-branched polyester, hyperbranched polyether or the hyperbranched poly esteramides that contain great amount of hydroxy group end functional group by a step or multistep is terminal-modified makes.
3. the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 2, it is characterized in that: described hyper-branched polyester is made by polymerization progressively by acid anhydrides or acid and dibasic alcohol, the preparation method is: add acid anhydrides or acid in reaction vessel, solvent and catalyzer, solvent adding amount is acid anhydrides or sour quality 2 times, catalytic amount is acid anhydrides or sour quality 0.001 times, stir, dripping dibasic alcohol under agitation condition reacts, temperature of reaction is controlled at-10 ℃～250 ℃, and the reaction times is 0.5～30 hour, after reaction finishes, product is precipitated with precipitation agent, throw out promptly obtains hyper-branched polyester 45 ℃～250 ℃ dryings
Wherein said acid anhydrides is that trimellitic acid 1,2-anhydride, acid are the dihydroxyalkyl propionic acid, and described dibasic alcohol is 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol or Diethylene Glycol; Described solvent is one or more in chloroform, methylene dichloride, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), the dimethyl formamide; Described catalyzer is one or more in hydrochloric acid, Phenylsulfonic acid, toluene sulfonic acide, sulfuric acid, potassium methylate, tetraethylammonium bromide, the boron trifluoride ethyl ether complex; Described precipitation agent is acetone, ether, tetrahydrofuran (THF) or their mixture.
4. the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 3, it is characterized in that: described hyper-branched polyester preparation feedback temperature is 0 ℃～200 ℃, and the reaction times is 0.5～25 hour.
5. the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 2, it is characterized in that: the hyper-branched polyester that contains terminal hydroxy group is by A
2And B
3Monomer is synthetic, at first A
2And B
3In B reaction generate AB
2Monomer further generates hyper-branched polyester, A from polycondensation then
2Monomer is a Succinic anhydried, Pyroglutaric acid, and Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride or substituent cyclic acid anhydride is arranged, the B3 monomer comprises TriMethylolPropane(TMP), glycerine, R-GLYCIDOL, glycerol, AB
2Monomer comprises the monomer that contains two hydroxyls of a carboxyl.
6, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 2, it is characterized in that: described hyperbranched polyether is by Racemic glycidol and TriMethylolPropane(TMP), perhaps glycidyl ether and TriMethylolPropane(TMP), perhaps glycidyl ether and 3-ethyl-3-methylol butylene oxide ring, perhaps glycidyl ether and 3-methyl-3-methylol butylene oxide ring, polycondensation or ring-opening polymerization form, method is in reaction vessel, add solvent and oxy-compound, solvent adding amount is 2 times of oxy-compound amount, logical nitrogen, drip Racemic glycidol or glycidyl ether, its amount is identical with the oxy-compound amount, temperature of reaction is controlled at-10 ℃～250 ℃, reaction times is 0.5～30 hour, after reaction finishes, product precipitates with precipitation agent, throw out promptly obtains hyperbranched polyether 25 ℃～70 ℃ dryings, and wherein said solvent is a chloroform, methylene dichloride, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), in the dimethyl formamide one or more; Used precipitation agent is acetone, ether, tetrahydrofuran (THF) or their mixture.
7, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 6 is characterized in that: described hyperbranched polyether preparation feedback temperature is 0 ℃～200 ℃, and the reaction times is 0.5～25 hour.
8, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 2, it is characterized in that: described hyperbranched poly esteramides is made by step-reaction polymerization by polynary azanol and acid anhydrides, method is to add polynary azanol in reaction vessel, solvent and catalyzer, their mol ratio is 1:2:0.005, drip the acid anhydrides of stoichiometric ratio, temperature of reaction is controlled at-10 ℃～250 ℃, reaction times is 0.5～30 hour, after reaction finishes, product is in the aqueous solution of sodium hydroxide and after purifying, drying at 25 ℃～200 ℃ promptly obtains the hyperbranched poly esteramides
Wherein, described polynary azanol comprises Tutofusin tris, diethanolamine, diisopropanolamine (DIPA); Described acid anhydrides comprises Succinic anhydried, Pyroglutaric acid, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, substituent cyclic acid anhydride is arranged; Described solvent is one or more in chloroform, methylene dichloride, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), the dimethyl formamide; Described catalyzer is one or more in hydrochloric acid, Phenylsulfonic acid, toluene sulfonic acide, sulfuric acid, potassium methylate, tetraethylammonium bromide, the boron trifluoride ethyl ether complex.
9, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 2, it is characterized in that: described hyper-branched polyester, it is to be the compound modified of thiazolinyl with end group directly that hyperbranched polyether or one step of hyperbranched poly esteramides are modified as hyperbranched many double bond monomers, feasible end has many pairs of keys, method is to add 10 parts of hyperbranched monomers by mass fraction in reaction vessel, 40 parts of solvents, 0.005 part of catalyzer tosic acid, 0.005 part of hydroquinone of polymerization retarder, logical nitrogen, drip the monomer reaction that contains thiazolinyl by stoichiometry, temperature of reaction is controlled at-10 ℃～200 ℃, reaction times is 0.5～20 hour, after reaction finishes, add the precipitation agent washing, obtain hyperbranched many double bond monomers 20 ℃～100 ℃ dryings, used end group is the double bond containing acid of compound for reacting with hydroxyl of thiazolinyl, acid anhydrides or acyl chlorides; Solvent is toluene, dimethylbenzene.
10, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 9, it is characterized in that: described hyper-branched polyester, hyperbranched polyether or hyperbranched poly esteramides and the monomeric temperature of reaction that contains thiazolinyl are at 0 ℃～150 ℃, and the reaction times is 0.5～15 hour.
11, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 10 is characterized in that: described properties-correcting agent is vinylformic acid, methacrylic acid, acrylate chloride.
12, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 2, it is characterized in that: the step that described hyper-branched polyester, hyperbranched polyether or hyperbranched poly esteramides multistep are modified as hyperbranched many double bond monomers is: the first step is an amido with the organic terminal groups modification of raw material, the intermediate of carboxyl or hydroxyl, when the hyperbranched polymer terminal groups modification is amido, with dimethylamine or diethylamine, under the condition of pressurization of heating and end group be the organism generation dehydration reaction of hydroxyl, generating end group is the tertiary amine intermediate; Further use the alkenyl monomer modification then, make that terminal group is a thiazolinyl, this goes on foot the vinyl carboxylic acid, chloro thiazolinyl alkane or the compound aromatic base that contain two keys of used properties-correcting agent for reacting with the end group after the first step modification, the modified-reaction temperature is-10 ℃～200 ℃, and the reaction times is 0.5～20 hour.
13, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 12 is characterized in that: described vinyl carboxylic acid is a vinylformic acid, methacrylic acid.
14, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 12 is characterized in that: described chloro thiazolinyl alkane is acrylate chloride.
15, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 12 is characterized in that: described compound aromatic base is p-chloromethyl styrene or glycidyl allyl ether.
16, the preparation method of maleic anhydride series polymer antisludging agent as claimed in claim 12 is characterized in that: described modified-reaction temperature is 0 ℃～150 ℃, and the reaction times is 0.5～15 hour.
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| CN103125482A (en) * | 2011-11-30 | 2013-06-05 | 安徽省蓝天化工有限公司 | Preparation method of sterilization and algae removal stripping agent |
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| CN102674567B (en) * | 2012-05-16 | 2013-11-20 | 东南大学 | Environment-friendly dendritic polyether dirt dispersion agent and preparation method thereof |
| CN102807285B (en) * | 2012-08-01 | 2013-11-20 | 东南大学 | Environment-friendly branched polyether water treatment agent and preparation method thereof |
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