CN101787095B - Method for preparing hyperbranched polymer by oxidation polymerization - Google Patents

Abstract

The invention relates to a method for preparing hyperbranched polymer by oxidation polymerization and belongs to the field of the polymer chemistry. The method uses vinyl monomer dimethylaminoethyl methacrylate as a monomer, uses an oxidizing agent as a catalyst and uses distilled water as a solvent, wherein the oxidizing agent is cupric salt and ferric salt; and a reaction system reacts for 30 minutes to 24 hours in a temperature range of between 0 and 60 DEG C to obtain the hyperbranched polymer PDMAEMA the molecular weight of which is between 3.03*104g. mol-1 and 2.17*105g.mol-1. The method adds the common and cheap higher oxidation state transition metal salts such as CuSO4 and the like into aqueous solution of DMAEMA, utilizes the characteristic that the inner electron transfer (ISET) has high reaction rate at lower temperature to react at a temperature close to the room temperature to obtain the hyperbranched PDMAEMA.

Description

A kind of method for preparing hyperbranched polymer through oxypolymerization

Technical field

The invention belongs to chemical field, relate to the preparation of radical polymerization technique and hyperbranched polymer.

Background technology

The notion of hyperbranched polymer is that Flory proposed in nineteen fifty-two: he points out AB _xThe monomeric polycondensation of (x>=2) type will generate the highly branched polymkeric substance of solubility, and this polymkeric substance is not perfect dendritic macromole, but defective hyperbranched polymer.1987; Does the Kim of Du Pont company etc. utilize the method for polycondensation at first to obtain first kind of hyperbranched polymer (Water-soluble hyperbranched polyphenylene:a-unimolecular micelle that industrial use is arranged? J.Am.Chem.Soc.; 1990,112:4592-4593; Hyperbranched polyphenylenes.Macromolecules, 1992,25:5561-5572; One-step synthesis of hyperbranched dendritic polyesters.J Am.Chem.Soc., 1991,113:4583-4588.).Nineteen ninety-five, the method that Fr é chet etc. has reported a kind of new synthesis of super branched polymkeric substance from the condensation vinyl polymerization (self-condensing vinyl polymerization, SCVP).Used monomer is AB ^*Type, wherein A is a vinyl, B ^*For causing the reactive group of vinyl polymerization.Monomer be initiator be again branch point, monomer activation under the effect of catalyzer produces a plurality of living radicals; Cause next step reaction; Along with the carrying out of polyreaction, branch point increases, and finally forms hyperbranched polymer (Self-Condensing Vinyl Polymerization:An Approach toDendritic Materials.Science; 1995,269:1080-1083; Synthesis of Branched and HyperbranchedPolystyrenes.Macromolecules, 1996,29:1079-1081; Preparation of HyperbranchedPolyacrylates by Atom Transfer Radical Polymerization.1.Acrylic AB*Monomers in " Living " Radical Polymerizations.Macromolecules; 1997,30:5192-5194).1992; Suzuki (Multibranching polymerization:palladium-catalyzed ring-opening polymerization of cycliccarbamate to produce hyperbranched dendritic polyamine.Macromolecules; 1992; 25:7071-7072) utilize ring-opening polymerization to obtain hyperbranched polyether, this polyreaction is a kind of many branching of original position process, and the quantity that the chain end group increases is carried out and increased with polymerization process.And Frey (Controlled Synthesis of HyperbranchedPolyglycerols by Ring-Opening Multibranching Polymerization.Macromolecules; 1999; 32:4240-4246) then utilize Racemic glycidol to carry out anionic ring-opening polymerization; It is controlled to have made molecular weight, the hyperbranched polyether that MWD is narrower.

Right that, we recognize that also above method all has following two shortcomings in varying degrees: (1) monomer source comparatively lacks, and the overwhelming majority is not common marketable material; (2) mostly polymerization method is active or accurate living polymerization, therefore polymerizing condition is all had strict demand, such as deoxygenation repeatedly etc.And these two shortcomings have seriously limited popularizing of above method.

The seventies in last century, people such as Otsu are just through proofs such as the free resonance power spectrums of electronics, with Cu (NO ₃) ₂Can tertiary amine be oxidized to-N-CH ₂Radical; And self is reduced; Reaction (the A study oninitiation of vinyl polymerization with diacyl peroxide-tertiary amine systems by spin trappingtechnique.Makromol Chem 1975 that shown among accompanying drawing Fig. 1 also promptly takes place; 176,561-571.).On the other hand, since the eighties in last century, Qiu Kunyuan etc. are verified in a series of activities, in peroxide-tertiary amine system, in the tertiary amine-N-CH ₂-R is oxidized to-the N-CH-R radical, and the latter can further cause the polymerization of vinyl monomer, and (substituted radical in the tertiary amine promotes the active influence of vinyl polymerization to it to form high molecular weight product.The polymer journal, 1991, (4): 493-497; Persulphate and N,N,N system cause the research of vinyl polymerization mechanism.The polymer journal, 1988, (2): 152-156; Cross-centennial polymer science-polymer chemistry, first version, Beijing: Chemical Industry Press calendar year 2001), shown in Figure 2 like accompanying drawing.In addition, Suzuki also proves, Cu ²⁺Or Ni ³⁺Can with in the tertiary amine-N-CH ₃Be oxidized to-N-CH ₂Radical (SuzukiM Acc Chem Res 2007,40 (7): 609-617).

Also can further extend by above result and to learn: for the DMAEMA that contains tertiary amine group, if there is Cu ²⁺In oxygenant, then: at first DMAEMA self can be oxidized to the monomer radical, causes the chainpropagation of other monomer molecule, and stops forming line style PDMAMEA chain through double-basis; Secondly, if two molecule DMAEMA monomer radical generation additions, this polymerization process then changes into from the radical polymerization of condensation vinyl, thereby obtains hyperbranched PDMAEMA; The the 3rd: Cu ²⁺Also can the dimethylamino on the PDMAEMA chain be oxidized to radical Deng oxidizer molecule, thereby cause the polymerization of DMAEMA, thereby obtain hyperbranched PDMAEMA from the PDMAEMA side group.This process such as accompanying drawing are shown in Figure 3.

Passable by above analysis, in this process, only need common and cheap CuSO ₄Add in the DMAEMA aqueous solution Deng high oxidation state transition metal salt; Wherein the adding of water is in order to promote the dissolving of high oxidation state transition metal salt in reaction system; Utilize inner electron to shift (ISET) and also have these characteristics of high reaction rate at a lower temperature; Near thermotonus room temperature can obtain hyperbranched PDMAEMA.

Summary of the invention

The invention discloses a kind of through oxidizer catalytic self reductibility vinyl monomer dimethylaminoethyl methacrylate (DMAEMA) oxypolymerization and obtain the method for branched polymer compound,

The step of this method is following: with vinyl monomer: dimethylaminoethyl methacrylate (DMAEMA) is catalyzer as monomer with the small amounts agent, and wherein said oxygenant is cupric salt, trivalent iron salt; Wherein the charging capacity ratio of the same dimethylaminoethyl methacrylate of oxygenant (DMAEMA) is 3.4 * 10 ^-2～3.5 * 10 ^-5With zero(ppm) water is solvent, and reaction system is in 0～60 ℃ of TR internal reaction 30min～24hr.Utilize oxygenant that the oxygenizement of the tertiary amine group in the monomer is formed the monomer radical, the latter is contained two keys and radical, and three direction chainpropagations in the past are 3.03 * 10 thereby obtain molecular weight ⁴Gmol ^-1～2.17 * 10 ⁵Gmol ^-1Hyperbranched polymer PDMAEMA;

Resulting polymers is measured absolute molecular weight by gas Chromatographic Determination monomer conversion, gel permeation chromatography relative molecular weight and MWD, multi-angle laser light scattering respectively.

Measure the relative molecular weight and the MWD of resulting polymers in the polymerization process respectively by gas Chromatographic Determination monomer conversion, gel permeation chromatography (GPC).The mensuration and the method for calculation of monomer conversion are following: adopt the Hangzhou GC-1690 of Ke Xiao company type GC, kapillary pillar length 30m, internal diameter 0.32mm; Carrier gas is a high pure nitrogen; Flow velocity 30mL/min, column temperature rises to 180 ℃, 10 ℃/min of temperature rise rate from 70 ℃; With methyl-sulphoxide or toluene is interior mark, measures differential responses monomer conversion constantly according to computes:

The transformation efficiency calculation formula of DMAEMA:

$\mathrm{Conv}.=1-\frac{B_t\&times;C_0}{{\mathrm{<figure-callout\; id="0"\; label="B"\; filenames="HSA00000049317900021.png"\; state="\{\{state\}\}">B</figure-callout>}}_0\&times;C_t}$ (formula 1)

In the formula 1 wherein, B ₀The peak area of DMAEMA in the gc elution profile in the expression zero moment reaction system, C ₀Mark (methyl-sulphoxide or toluene) peak area in the gc elution profile in the expression zero moment reaction system; B _tThe peak area of DMAEMA in the gc elution profile in the expression t moment reaction system, C _tThe peak area of DMAEMA in the gc elution profile in the expression t moment reaction system.

Adopt GPC to measure the relative molecular weight and the MWD of polymkeric substance, comprise relative number average molecular weight (M _n), relative weight-average molecular weight (M _w) and MWD (PDI, i.e. M _w/ M _n); The GPC device comprises Waters 1515 type HPLC pumps, 2414 RI detectors, 717 type automatic samplers, Styrage HR 4e; HR 1, HR 0.5 chromatographic column and Breeze workstation; 35 ℃ of column temperatures, moving phase are THF (THF), flow velocity 1mL/min, are that standard specimen is calibrated with the monodisperse polystyrene.PDMAEMA has dissaving structure for the checking gained, also measures the absolute molecular weight and the intrinsic viscosity of sample segment respectively, because generally speaking; The intrinsic viscosity of simple linear polymer in dilute solution meets MHS equation ([η]=K * M) with the relation between the molecular weight; Also be that ln [η]～lnM is linear, hyperbranched polymer then presents downward para-curve, also is that the slope of hyperbranched polymer ln [η]～lnM in dilute solution descends along with the increase of molecular weight gradually; And (Luo Yunjun, Tan Huimin gradually descend along with the increase of the degree of branching; Hyperbranched polymer, Beijing: Chemical Industry Press, 2005; P90-92).Absolute molecular weight and intrinsic viscosity are by measuring with the placed in-line Wyatt miniDAWN of GPC triangle laser light scattering detector (MALLS) and the online viscosity detector of Wyatt Viscostar, and all data are by the WyattASTRA software processes.Used refractive index increment (dn/dc) is 0.100mLg when calculating absolute weight-average molecular weight through light scattering data ^-1

Technological merit of the present invention: with common and cheap CuSO ₄Add in the DMAEMA aqueous solution Deng high oxidation state transition metal salt, utilize out-shell electron to shift (OSET) and also have these characteristics of high reaction rate at a lower temperature, near thermotonus room temperature can obtain hyperbranched PDMAEMA.

Description of drawings

Wherein Fig. 1 is Cu (NO ₃) ₂-tertiary amine redox reaction formula;

Fig. 2 is peroxy compound-tertiary amine redox processes reaction formula;

Fig. 3 is Cu ²⁺The radical polymerization of catalysis DMAEMA prepares hyperbranched PDMAEMA reaction principle figure.

Embodiment

To combine the embodiment of different condition to come the present invention done below and further describe, following examples should be regarded as the specializing of claim, but not dwindle and limit.

Embodiment one: with CuSO ₄(0.5g, 0.002mol), DMAEMA (10mL, 0.0539mol) with a small amount of in mark methyl-sulphoxide (DMSO) add in the beaker and shake up, airtight after the deoxygenation, and utilize water-bath to make its temperature of reaction be controlled at 30 ℃, behind the 6hr, GC is surveyed in sampling, recording transformation efficiency is 61.1%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to be made into concentration be 1% solution, and it is 2.17 * 10 that GPC records relative molecular weight ⁵Gmol ^-1, it is 1.26 * 10 that MALLS measures absolute molecular weight ⁶Gmol ^-1

Embodiment two: with CuSO ₄(1.3mg, 0.0052mmol), DMAEMA (25mL, 0.1500mol), deionized water (25mL) and a small amount of DMSO join in the round-bottomed flask; Airtight after the deoxygenation, and utilize water-bath to make its temperature of reaction be controlled at 30 ℃, behind the 30min; GC is surveyed in sampling, and recording transformation efficiency is 9.0%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to be made into concentration be 1% solution, and it is 3.03 * 10 that GPC records relative molecular weight ⁴Gmol ^-1

Embodiment three: with CuSO ₄(1.0mg, 0.0040mmol), thick DMAEMA (20mL, 0.1100mol), deionized water (20mL) and interior mark DMSO join in the round-bottomed flask; Airtight after the deoxygenation, and utilize water-bath to make its temperature of reaction be controlled at 30 ℃, behind the 8hr; GC is surveyed in sampling, and recording transformation efficiency is 84.7%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to be made into concentration be 1% solution, and it is 1.13 * 10 that GPC records relative molecular weight ⁵Gmol ^-1, absolute molecular weight is 1.17 * 10 ⁶Gmol ^-1

Embodiment four: with CuSO ₄(6.3mg, 0.0252mmol), DMAEMA (5mL, 0.0270mol) and deionized water (20mL) add in the beaker and shake up; Take out 2mL and pour in the round-bottomed flask, add DMAEMA (3.6mL, 0.0194mol), deionized water (14.4mL) dilution; Mark DMSO is airtight after the deoxygenation in adding again, and utilizes water-bath to make its temperature of reaction be controlled at 30 ℃; Behind the 24hr, GC is surveyed in sampling, and recording transformation efficiency is 34.4%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to become concentration be 1% solution, and it is 7.15 * 10 that GPC records relative molecular weight ⁴Gmol ^-1

Embodiment five: with CuSO ₄(1.3mg, 0.0052mmol), DMAEMA (25mL, 0.1500mol), deionized water (25mL) and interior mark DMSO join in the round-bottomed flask; Airtight after the deoxygenation, utilize mixture of ice and water to make its temperature of reaction be controlled at 0 ℃, behind the 16hr; GC is surveyed in sampling, and recording transformation efficiency is 8.9%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to be made into concentration be 1% solution, and it is 1.26 * 10 that GPC surveys relative molecular weight ⁵Gmol ^-1, absolute molecular weight is 9.34 * 10 ⁵Gmol ^-1

Embodiment six: with CuSO ₄(5.0mg, 0.0200mmol), DMAEMA (18mL, 0.0971mol), deionized water (2mL) and interior mark DMSO add in the beaker and shake up; Airtight after the deoxygenation, and utilize oil bath to make its temperature of reaction be controlled at 60 ℃, behind the 2hr; GC is surveyed in sampling, and recording transformation efficiency is 68.3%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to be made into concentration be 1% solution, and it is 4.91 * 10 that GPC records relative molecular weight ⁴Gmol ^-1, absolute molecular weight is 1.62 * 10 ⁵Gmol ^-1

Embodiment seven: with FeCl ₃(1.6mg, 0.0099mmol), DMAEMA (10mL, 0.0539mol), deionized water (10mL) and interior mark DMSO add in the beaker and shake up; Airtight after the deoxygenation, and utilize water-bath to make its temperature of reaction be controlled at 60 ℃, behind the 24hr; GC is surveyed in sampling, and recording transformation efficiency is 79.8%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to be made into concentration be 1% solution, and it is 1.46 * 10 that GPC records relative molecular weight ⁵Gmol ^-1, absolute molecular weight is 2.55 * 10 ⁶Gmol ^-1

Embodiment eight: with CuBr ₂(2.8mg, 0.0125mmol), DMAEMA (5mL, 0.0297mol), deionized water (20mL) and interior mark DMSO add in the beaker and shake up; Airtight after the deoxygenation, and utilize water-bath to make its temperature of reaction be controlled at 30 ℃, behind the 12hr; GC is surveyed in sampling, and recording transformation efficiency is 67.0%.Polymers soln is put into 70 ℃ of water-baths, treat polymer precipitation after, it is taken out the deionized water put into room temperature again; Be transferred to then in 70 ℃ of water-baths; So re-treatment is more than three times, with the polymkeric substance after filtering be placed in the baking oven in 45 ℃ dry 2 days down, promptly obtain white or faint yellow product; Product is dissolved in THF, and to be made into concentration be 1% solution, and it is 4.56 * 10 that GPC records relative molecular weight ⁴Gmol ^-1, absolute molecular weight is 1.02 * 10 ⁶Gmol ^-1

Claims (1)

1. method for preparing hyperbranched polymer through oxypolymerization; It is characterized in that with the vinyl monomer dimethylaminoethyl methacrylate as monomer; With the oxygenant is catalyzer, is solvent with zero(ppm) water, and wherein said oxygenant is cupric salt, trivalent iron salt; Wherein oxygenant is 3.4 * 10 with the charging capacity ratio of dimethylaminoethyl methacrylate DMAEMA ^-2～3.5 * 10 ^-5Reaction system is in 0～60 ℃ of TR internal reaction 30min～24hr, and obtaining molecular weight is 3.03 * 10 ⁴Gmol ^-1～2.17 * 10 ⁵Gmol ^-1Hyperbranched polymer PDMAEMA.

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