CN100418992C - Process for preparing hydrophilic-hydrophobic graft polymer with controllable main and side chain length - Google Patents
Process for preparing hydrophilic-hydrophobic graft polymer with controllable main and side chain length Download PDFInfo
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- CN100418992C CN100418992C CNB2006100398300A CN200610039830A CN100418992C CN 100418992 C CN100418992 C CN 100418992C CN B2006100398300 A CNB2006100398300 A CN B2006100398300A CN 200610039830 A CN200610039830 A CN 200610039830A CN 100418992 C CN100418992 C CN 100418992C
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- hydrophobic
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Abstract
The present invention relates to a preparation method for a hydrophilic-hydrophobic graft polymer whose main chain length and side chain length can be controlled, which belongs to the field of graft polymer preparation technologies. A hydrophobic macromolecular chain of polystyrene (PSt) and polyacrylate is synthesized by an atom transfer radical polymerization method, wherein the molecular weight distribution of the hydrophobic macromolecular chain is smaller than or equal to 1.2. Through a hydrolysis reaction under an acid condition, a polymethacrylic acid or polyacrylic acid hydrophilic macromolecular chain is obtained, wherein the relative molecular weight of the hydrophilic macromolecular chain is controllable, and distribution is narrow. A halogen atom on the tail end of the hydrophobic macromolecular chain is used for carrying out a nucleophilic substitution reaction with a carboxyl group on a side group of the hydrophilic macromolecular chain in a solution so as to 'assemble' the hydrophobic chain onto the hydrophilic chain to form the hydrophilic-hydrophobic graft polymer. The length of the macromolecular chains can be controlled by regulating the compounding ratio of an initiating agent to monomers. The hydrophilic chains of different length are used as main chains, and the hydrophobic chains of different length are used for the 'assembly', which can prepare the hydrophilic-hydrophobic graft polymers whose main chain length and side chain length can be controlled.
Description
Technical field
The preparation method of the hydrophilic-hydrophobic graft polymer that a kind of master, side chain length are controlled belongs to the graftomer preparing technical field.The hydrophobicity macromolecular chain controlled by atom transfer radical polymerization method synthetic molecules chain length, that end contains halogen atom, by hydrolysis polymethyl tert-butyl acrylate under acidic conditions (or polyacrylic acid tert-butyl ester) preparation polymethyl acrylic acid (or polyacrylic acid), the proportioning of monomer and initiator is controlled the length of hydrophobicity macromolecular chain in the change atom transfer radical polymerization, and the above-mentioned hydrophobicity macromolecular chain hydrolysis of selection different lengths can obtain having polymethyl acrylic acid (or polyacrylic acid) the wetting ability macromolecular chain of different lengths; Nucleophilic substitution reaction success " assembling " between the halogen atom by hydrophobicity macromolecular chain end and the carboxyl of wetting ability macromolecular chain side group graftomer.This hydrophilic-hydrophobic polymkeric substance can further carry out the nucleocapsid structure microballoon that self-assembly forms tactical rule in selective solvent, change the ratio and the length of hydrophobic chain and hydrophilic chain, can reach the purpose that changes microballoon size and surperficial carboxyl-content.
Background technology
Graftomer can carry out self-assembly and form stable particle in specific solvent, having broad application prospects aspect drug conveying and release, the functionalization material.Graftomer can be prepared by several different methods, but be difficult to obtain regular polymer sometimes by simple polyreaction, in macromolecular chain, introduce the method for required small molecules or macromolecular structure by the interaction between macromolecular chain and the molecule, obtain research gradually and use.Atom transfer radical polymerization (ATRP) is a kind of polymerization process that rose in recent years, can access the polymkeric substance that relative molecular mass is controlled, the relative molecular mass distribution is very narrow by the ATRP method, be the ideal selection that preparation contains the special groups polymkeric substance, as obtain the molecular chain that end contains a halogen atom (chlorine or bromine atom).The present invention utilizes the side group carboxyl of the polymethyl acrylic acid (or polyacrylic acid) that the halogen atom of hydrophobicity macromolecular chain end and hydrolysis obtain to carry out nucleophilic substitution, realization is with the purpose of hydrophobicity macromolecular chain " assembling " on the hydrophilic backbone, preparing with wetting ability polymethyl acrylic acid or polyacrylic acid is trunk, and the hydrophobicity macromolecular chain is the hydrophilic-hydrophobic graft polymer of side shoot.
Summary of the invention
The preparation method who the purpose of this invention is to provide the controlled hydrophilic-hydrophobic graft polymer of a kind of master, side chain length, by atom transfer radical polymerization method, the controlled hydrophobicity macromolecular chain of synthetic molecular weight respectively; Because the side group tertiary butyl facile hydrolysis of methacrylic tert-butyl acrylate or tert-butyl acrylate changes carboxyl into, obtain the wetting ability macromolecular chain polymethyl acrylic acid or the polyacrylic acid of length controlled by hydrolysis polymethyl tert-butyl acrylate or tert-butyl acrylate under acidic conditions, proceed nucleophilic substitution reaction and prepare main chain, the controlled hydrophilic-hydrophobic graft polymer of side chain lengths.
Technical scheme of the present invention:
By Transfer Radical Polymerization synthetic polystyrene PSt or polyacrylate(s) (polymetylmethacrylate, polymethyl tert-butyl acrylate PtBMA, polyacrylic acid tert-butyl ester PtBA, Vinalac 5920 PnBMA, the positive butyl ester PnBA of polyacrylic acid etc.) hydrophobicity macromolecular chain; By making PtBMA or PtBA hydrolysis under acidic conditions, obtain polymethyl acrylic acid PMAA or polyacrylic acid PAA wetting ability macromolecular chain; Utilize the halogen atom of hydrophobicity macromolecular chain end and the carboxyl on the wetting ability macromolecular chain side group to carry out nucleophilic substitution reaction in solution, form hydrophilic-hydrophobic graft polymer, its general formula is:
In the formula, 20≤n≤200,20≤m≤200, p represents the replacement degree, the scope of p is 5%-20%.R is H, CH
3, R
1For
COOCH
3, COOC (CH
3)
3, COO (CH
2)
3CH
3R
2Be H, CH
3
The preparation of hydrophobicity macromolecular chain, its reaction formula is as follows:
X is Cl or Br in the formula.
Atom transfer radical polymerization method is to utilize halide-containing (theoretically, contain the haloalkane or the aromatic sulfonyl chloride class material of inducing the conjugation group on the α position and all can make the ATRP initiator), in the coordination system of transition metal and coordination compound formation, realize the quick balance of dormancy kind and spike, thereby make monomer polymerization, it can finish reaction under relatively mild condition, and polyreaction is stable, can obtain the very narrow polymkeric substance of relative molecular mass distribution.Molecular weight of polymer directly depends on the mol ratio of monomer and initiator in the ATRP reaction.
The preparation method of hydrophobicity macromolecular chain, be to be polymerization single polymerization monomer with the hydrophobic monomer, selection has the initiator of ad hoc structure, in the presence of coordination agent and catalyzer, carry out atom transition free radical polymerization reaction and make the hydrophobicity macromolecular chain, change the relative molecular mass of the mol ratio control macromolecular chain of monomer and initiator.
Concrete preparation technology is: be polymerization single polymerization monomer with the hydrophobic monomer, select to contain the haloalkane or the aromatic sulfonyl chloride class material of inducing the conjugation group on the α position and make initiator, in the presence of coordination agent and catalyzer, carry out atom transition free radical polymerization reaction and make polystyrene or the polyacrylate(s) hydrophobicity macromolecular chain that end contains halogen atom, polymerization single polymerization monomer: coordination agent: catalyzer: the mole proportioning of initiator is decided to be n: 1: 2: 1, mol ratio 20≤n≤200 that change monomer and initiator reach the relative molecular mass of control macromolecular chain, temperature of reaction is controlled at 80～130 ℃, reaction times is controlled to be 6～12 hours, coordination agent is a Tetramethyl Ethylene Diamine, five methyl diethylentriamine or bipyridine, catalyzer is a cuprous chloride, cuprous bromide or iron protochloride, described initiator are alpha-brominated methyl propionate or ethyl-alpha-bromopropionate.
The preparation method of wetting ability macromolecular chain PMAA: be to be that raw material is hydrolyzed with PtBMA, select 1, the 4-dioxane is dissolution with solvents PtBMA, adds a certain amount of concentrated hydrochloric acid and refluxes.Hydrolysising reacting temperature is controlled at 75～95 ℃, and the reaction times is controlled to be 12～40 hours, and reaction finishes, and drips hexanaphthene or normal hexane and makes it precipitation, suction filtration, obtains hydrolysate, concentrated hydrochloric acid and 1, and the volume ratio of 4-dioxane is 1: 10～1: 20.
The preparation method of wetting ability macromolecular chain PAA: be to be that raw material is hydrolyzed with PtBA, selecting methyl-sulphoxide is dissolution with solvents PtBA, adds a certain amount of concentrated hydrochloric acid and refluxes.Hydrolysising reacting temperature is controlled at 85～95 ℃, and the reaction times is controlled to be 20～40 hours, and reaction finishes, and drips sherwood oil or normal hexane and makes it precipitation, suction filtration, obtains hydrolysate, and the volume ratio of concentrated hydrochloric acid and methyl-sulphoxide is 1: 10～1: 20.
Synthesizing of hydrophilic-hydrophobic graft polymer: in reaction vessel, add PMAA or PAA successively, a certain amount of hydrophobicity macromolecular chain, with N, dinethylformamide is a solvent, stir fully, the triethylamine that the 1-5 of adding hydrophobicity macromolecular chain mole number doubly measures, temperature of reaction is controlled to be 30～50 ℃, reaction times is controlled to be 6～20 hours, and reaction finishes the back naturally cooling, leaves standstill, collect layer oily matter, use a certain amount of chloroform or tetrahydrofuran (THF) repetitive scrubbing again, remove unreacted polymer, obtain hydrophilic-hydrophobic graft polymer.Its reaction formula is as follows:
Wherein R is H, R
1For
R
2=CH
3The time, described hydrophilic-hydrophobic graft polymer is polymethyl acrylic acid-g-polystyrene graft polymkeric substance.
Wherein R is H, R
1Be COOC (CH
3)
3, R
2=CH
3The time, described hydrophilic-hydrophobic graft polymer is polymethyl acrylic acid-g-polyacrylic acid tert-butyl ester graftomer.
Wherein R is CH
3, R
1Be COOC (CH
3)
3, R
2=CH
3The time, described hydrophilic-hydrophobic graft polymer is polymethyl acrylic acid-g-polymethyl tert-butyl acrylate graftomer.
Wherein R is CH
3, R
1Be COOCH
3, R
2=CH
3The time, described hydrophilic-hydrophobic graft polymer is polymethyl acrylic acid-g-polymethylmethacrylate graftomer.
Wherein R is CH
3, R
1Be COO (CH
2)
3CH
3, R
2=CH
3The time, described hydrophilic-hydrophobic graft polymer is polymethyl acrylic acid-g-Vinalac 5920 graftomer.
Wherein R is H, R
1For
R
2During=H, described hydrophilic-hydrophobic graft polymer is polyacrylic acid-g-polystyrene graft polymkeric substance.
Wherein R is H, R
1Be COOC (CH
3)
3, R
2During=H, described hydrophilic-hydrophobic graft polymer is polyacrylic acid-g-polyacrylic acid tert-butyl ester graftomer.
Wherein R is CH
3, R
1Be COOC (CH
3)
3, R
2During=H, described hydrophilic-hydrophobic graft polymer is polyacrylic acid-g-polymethyl tert-butyl acrylate graftomer.
Wherein R is CH
3, R
1Be COOCH
3, R
2During=H, described hydrophilic-hydrophobic graft polymer is polyacrylic acid-g-polymethylmethacrylate graftomer.
Wherein R is CH
3, R
1Be COO (CH
2)
3CH
3, R
2During=H, described hydrophilic-hydrophobic graft polymer is polyacrylic acid-g-Vinalac 5920 graftomer.
In the above-mentioned nucleophilic substitution reaction, the hydrophobic chain of selecting for use PMAA with different lengths or PAA to do main chain, different lengths is made side chain, can obtain main chain, hydrophilic-hydrophobic graft polymer that side chain lengths is different.
Through characterizing, all kinds of macromolecular chain molecular weight are controlled, the relative molecular mass (M that is evenly distributed
w/ M
n＜1.20).Can be by changing the relative molecular mass of controlled all kinds of macromolecular chains mole recently of monomer and initiator.All kinds of hydrophilic-hydrophobic graft polymer structures are clear and definite, and the grafting degree is tending towards saturated.
Beneficial effect of the present invention: the invention provides a kind of method for preparing the controlled hydrophilic-hydrophobic graft polymer of main chain, side chain length.The hydrophobic polypropylene esters of gallic acid or the polystyrene macromolecular chain that have synthesized relative molecular mass distribution≤1.2 by atom transfer radical polymerization; Can control the relative molecular mass of various macromolecular chains by regulating initiator and monomeric proportioning, that is molecular chain length is controlled.And then the hydrolysis under acidic conditions of polyacrylate(s) macromolecular chain, made the PMAA or the PAA of relative molecular mass narrowly distributing.In solution, utilize the halogen atom of hydrophobicity macromolecular chain end and the carboxyl on the wetting ability chain side group to carry out nucleophilic substitution reaction, hydrophobic chain " assembling " is formed graftomer to the wetting ability chain, can realize the preliminary controllability of a chain number.
Embodiment
Embodiment 1, hydrophobicity macromolecular chain PtBMA's is synthetic
In container, add five methyl diethylentriamine, CuCl, ethyl-alpha-bromopropionate, monomer (is 50 according to relative molecular mass needs n) by proportioning successively under the room temperature.Stirring makes it thorough mixing, through 1-5 freezing, thaw cycles, seals after continuing to feed high pure nitrogen 20-60min.Reaction is 6 hours in 100 ℃ of oil baths, take out, naturally cooling with tetrahydrofuran (THF) solubilizing reaction product, passes through the metal oxide glass post with solution, remove residual CuCl, (the methanol volume ratio is 1: 1-1: precipitate in the blending agent 5), filter repeatable operation to drip methanol, vacuum-drying gets PtBMA to constant weight.
Embodiment 2, hydrophobicity macromolecular chain PSt's is synthetic
In reaction vessel, add bipyridine, CuBr, alpha-brominated methyl propionate, monomer (is 200 according to relative molecular mass needs n) by proportioning successively under the room temperature.Stirring makes it thorough mixing, through freezing, the thaw cycles of several, seals after continuing to feed high pure nitrogen 45min.Reaction is 10 hours in 130 ℃ of oil baths, takes out, and naturally cooling is with hexanaphthene solubilizing reaction product, solution with alumina powder mixing, washing, filtration, is removed residual CuBr, drip in the ethanol medium and precipitate, filter, repeatable operation three times, vacuum-drying get PSt to constant weight.
Embodiment 3, hydrophobicity macromolecular chain PMMA's is synthetic
In container, add Tetramethyl Ethylene Diamine, FeCl by proportioning successively under the room temperature
2, alpha-brominated methyl propionate, monomer (is 100 according to relative molecular mass needs n).Stirring makes it thorough mixing, through freezing, the thaw cycles of several, seals after continuing to feed high pure nitrogen 60min.Reaction is 8 hours in 80 ℃ of oil baths, take out, and naturally cooling, with N, dinethylformamide solubilizing reaction product by the alumina glass post, is removed residual FeCl with solution
2, drip ethanol/water (the ethanol/water volume ratio is 1: 3-1: precipitate in the blending agent 5), filter, repeatable operation three times, vacuum-drying is to constant weight, PMMA.
Embodiment 4, hydrophobicity macromolecular chain PtBA's is synthetic
In flask, add Tetramethyl Ethylene Diamine, CuCl, ethyl-alpha-bromopropionate, monomer (is 20 according to relative molecular mass needs n) by proportioning successively under the room temperature.Stirring makes it thorough mixing, through freezing, thaw cycles, seals after continuing to feed high pure nitrogen 60min.Reaction is 12 hours in 100 ℃ of oil baths, finish the back naturally cooling, with tetrahydrofuran (THF) solubilizing reaction product, solution with alumina powder mixing, washing, filtration, is removed residual CuCl, and (the methanol volume ratio is 1: 1-1: precipitate in the blending agent 5) to drip methanol, filter, repeatable operation three times, vacuum-drying get PtBA to constant weight.
Embodiment 5, hydrophobicity macromolecular chain PnBA's is synthetic
In flask, add five methyl diethylentriamine, CuBr, alpha-brominated methyl propionate, monomer (is 75 according to relative molecular mass needs n) by proportioning successively under the room temperature.Stir fully,, seal after continuing to feed high pure nitrogen 60min through freezing, thaw cycles.Reaction is 9 hours in 90 ℃ of oil baths, finish the back naturally cooling, with methyl-sulphoxide solubilizing reaction product, solution is washed with alumina powder, remove the metal remained composition, (the methanol volume ratio is 1: 1-1: precipitate in the blending agent 5) to drip methanol, filter, repeatable operation three times, vacuum-drying get PnBA to constant weight.
Embodiment 6, hydrophobicity macromolecular chain PnBMA's is synthetic
In flask, add bipyridine, CuCl, ethyl-alpha-bromopropionate, monomer (is 125 according to relative molecular mass needs n) by proportioning successively under the room temperature.Stir fully,, seal after continuing to feed high pure nitrogen 60min through freezing, thaw cycles.Reaction is 9 hours in 85 ℃ of oil baths, finish the back naturally cooling, with DMSO solubilizing reaction product, with the alumina powder washing, remove the metal remained composition, (the methanol volume ratio is 1: 1-1: precipitate in the blending agent 5) to drip methanol, filter, repeatable operation three times, vacuum-drying get PnBMA to constant weight.
Synthesizing of embodiment 7, wetting ability macromolecular chain
In flask, add PtBMA 1g, with 30mL 1, the dissolving of 4-dioxane, add the 1.5-3mL concentrated hydrochloric acid again, under 75-95 ℃ of temperature in the oil bath back flow reaction 12-40 hour, finish the back and take out sample, drip hexanaphthene or normal hexane and make it precipitation, suction filtration, vacuum-drying gets hydrolysate to constant weight.
Synthesizing of embodiment 8, wetting ability macromolecular chain
In flask, add PtBA 1g,, add the 1.5-3mL concentrated hydrochloric acid again with the dissolving of 30mL methyl-sulphoxide, under 85-95 ℃ of temperature in the oil bath back flow reaction 20-40 hour, finish the back and take out sample, drip sherwood oil or normal hexane and make it precipitation, suction filtration, vacuum-drying gets hydrolysate to constant weight.
The preparation of embodiment 9, hydrophilic-hydrophobic graft polymer
In container, add the PMAA or the PAA that obtain by embodiment 7 or example 8 hydrolysis successively, the hydrophobicity macromolecular chain of predetermined amount, DMF 5～20mL, stir, dissolve, add triethylamine 1～5mL, be warming up to 30～50 ℃ of reactions 6～20 hours, cool off, leave standstill, collect layer oily matter.Use a certain amount of chloroform or tetrahydrofuran (THF) repetitive scrubbing again, remove unreacted polymer, obtain hydrophilic-hydrophobic graft polymer.
Claims (7)
1. the preparation method of the controlled hydrophilic-hydrophobic graft polymer of a master, side chain length is characterized in that being contained by the synthetic end of Transfer Radical Polymerization the polystyrene PSt or the polyacrylate(s) hydrophobicity macromolecular chain of halogen atom; By making polymethyl tert-butyl acrylate PtBMA or polyacrylic acid tert-butyl ester PtBA hydrolysis under acidic conditions, obtain polymethyl acrylic acid PMAA or polyacrylic acid PAA wetting ability macromolecular chain; Utilize the halogen atom of hydrophobicity macromolecular chain end and the carboxyl on the wetting ability macromolecular chain side group to carry out nucleophilic substitution reaction in solution, form hydrophilic-hydrophobic graft polymer, its general formula is:
In the formula, 20≤n≤200,20≤m≤200, p represents the replacement degree, and the scope of p is 5%-20%, and R is H or CH
3, R
1For
COOCH
3, COOC (CH
3)
3Or COO (CH
2)
3CH
3, R
2Be H or CH
3
Described polyacrylate(s) is selected from polymetylmethacrylate, polymethyl tert-butyl acrylate PtBMA, polyacrylic acid tert-butyl ester PtBA, Vinalac 5920 PnBMA or the positive butyl ester PnBA of polyacrylic acid.
2. the preparation method of hydrophilic-hydrophobic graft polymer according to claim 1, it is characterized in that the preparation of hydrophobicity macromolecular chain: with vinylbenzene or esters of acrylic acid hydrophobic monomer is polymerization single polymerization monomer, select to contain the haloalkane or the aromatic sulfonyl chloride class material of inducing the conjugation group on the α position and make initiator, in the presence of coordination agent and catalyzer, carry out atom transition free radical polymerization reaction and make polystyrene or the polyacrylate(s) macromolecular chain that end contains halogen atom, polymerization single polymerization monomer: coordination agent: catalyzer: the mole proportioning of initiator is decided to be n: 1: 2: 1, mol ratio 20≤n≤200 that change monomer and initiator reach the relative molecular mass of control macromolecular chain, temperature of reaction is controlled at 80～130 ℃, reaction times is controlled to be 6～12 hours, coordination agent is a Tetramethyl Ethylene Diamine, five methyl diethylentriamine or bipyridine, catalyzer are cuprous chloride, cuprous bromide or iron protochloride.
3. the preparation method of hydrophilic-hydrophobic graft polymer according to claim 1 is characterized in that described initiator is alpha-brominated methyl propionate or ethyl-alpha-bromopropionate.
4. the preparation method of hydrophilic-hydrophobic graft polymer according to claim 1, it is characterized in that hydrolysis prepares wetting ability macromolecular chain PMAA: PtBMA is hydrolyzed, select 1, the 4-dioxane is dissolution with solvents PtBMA, adding a certain amount of concentrated hydrochloric acid refluxes, hydrolysising reacting temperature is controlled at 75～95 ℃, reaction times is controlled to be 12～40 hours, reaction finishes, drip hexanaphthene or normal hexane and make it precipitation, suction filtration, obtain hydrolysate, concentrated hydrochloric acid and 1, the volume ratio of 4-dioxane is 1: 10～1: 20.
5. the preparation method of hydrophilic-hydrophobic graft polymer according to claim 1, it is characterized in that hydrolysis prepares wetting ability macromolecular chain PAA: PtBA is hydrolyzed, selecting methyl-sulphoxide is dissolution with solvents PtBA, adding a certain amount of concentrated hydrochloric acid refluxes, hydrolysising reacting temperature is controlled at 85～95 ℃, reaction times is controlled to be 20～40 hours, reaction finishes, drip sherwood oil or normal hexane and make it precipitation, suction filtration, obtain hydrolysate, the volume ratio of concentrated hydrochloric acid and methyl-sulphoxide is 1: 10～1: 20.
6. the preparation method of hydrophilic-hydrophobic graft polymer according to claim 1, it is characterized in that the synthetic of hydrophilic-hydrophobic graft polymer: in reaction vessel, add PMAA or PAA successively, a certain amount of hydrophobicity macromolecular chain, with N, dinethylformamide is a solvent, stir fully, the triethylamine that the 1-5 of adding hydrophobicity macromolecular chain mole number doubly measures, temperature of reaction is controlled to be 30～50 ℃, and the reaction times is controlled to be 6～20 hours, reaction finishes the back naturally cooling, leave standstill, collect layer oily matter, use a certain amount of chloroform or tetrahydrofuran (THF) repetitive scrubbing again, remove unreacted polymer, obtain hydrophilic-hydrophobic graft polymer.
7. use the hydrophilic-hydrophobic graft polymer of the described preparation method's preparation of claim 1, it is characterized in that hydrophilic-hydrophobic graft polymer is selected from: polymethyl acrylic acid-g-polystyrene graft polymkeric substance, polymethyl acrylic acid-g-polyacrylic acid tert-butyl ester graftomer, polymethyl acrylic acid-g-polymethyl tert-butyl acrylate graftomer, polymethyl acrylic acid-g-polymethylmethacrylate graftomer, polymethyl acrylic acid-g-Vinalac 5920 graftomer, polyacrylic acid-g-polystyrene graft polymkeric substance, polyacrylic acid-g-polyacrylic acid tert-butyl ester graftomer, polyacrylic acid-g-polymethyl tert-butyl acrylate graftomer, polyacrylic acid-g-polymethylmethacrylate graftomer, or polyacrylic acid-g-Vinalac 5920 graftomer.
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| CN107903348B (en) * | 2017-11-28 | 2020-06-26 | 常州大学 | Preparation method of polyethylene glycol grafted polymethyl methacrylate amphiphilic graft copolymer |
| CN109574743A (en) * | 2018-11-26 | 2019-04-05 | 无锡市天膜新材料有限公司 | A kind of Water Soluble Compound fertilizer anti-caking agent and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| 两亲性嵌段共聚物PS-b-PMAA的合成与胶束化行为研究. 华慢，杨伟，薛乔，陈明清，刘晓亚，杨成.化学学报，第63卷第7期. 2005 |
| 两亲性嵌段共聚物PS-b-PMAA的合成与胶束化行为研究. 华慢，杨伟，薛乔，陈明清，刘晓亚，杨成.化学学报，第63卷第7期. 2005 * |
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Assignee: Jiangsu Guoli Chemical Technology Co., Ltd. Assignor: Jiangnan University Contract fulfillment period: 2009.3.15 to 2014.3.14 contract change Contract record no.: 2009320000657 Denomination of invention: Process for preparing hydrophilic-hydrophobic graft polymer with controllable main and side chain length Granted publication date: 20080917 License type: Exclusive license Record date: 2009.4.22 |
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