CN102432722A - Method for preparing rosin-based regular polymers - Google Patents
Method for preparing rosin-based regular polymers Download PDFInfo
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- CN102432722A CN102432722A CN2011103009502A CN201110300950A CN102432722A CN 102432722 A CN102432722 A CN 102432722A CN 2011103009502 A CN2011103009502 A CN 2011103009502A CN 201110300950 A CN201110300950 A CN 201110300950A CN 102432722 A CN102432722 A CN 102432722A
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Abstract
The invention discloses a method for preparing rosin-based regular polymers. The method comprises the following steps of: dissolving a rosin-based monomer, an initiator for free radical polymerization, and a reversible addition-fragmentation chain transfer reagent in a certain molar mass ratio in a solvent, introducing nitrogen to remove oxygen, reacting at the temperature of between 50 and 120 DEG C for 1 to 24h, precipitating polymers in methanol, and filtering and drying to obtain rosin-based polymers with different molecular weights, wherein the rosin-based monomer is a rosin derivative which can be subjected to free radical polymerization reaction. By the method, the rosin-based regular polymers with different molecular weights and molecular weight distributions (PDI) can be obtained. The polymers are taken as prepolymers of a functional rosin block polymer.
Description
Technical field
The present invention relates to a kind of preparation method of rosinyl regular polymer, particularly a kind of new polymerization method is used at rosinyl polymkeric substance synthetic.
Background technology
Rosin is a kind of important renewable data, also is one of main afforestation product of China, and world's rosin YO is about 1,200,000 tons, about 800,000 tons of China's rosin YO.Mainly by wanting resinous acid and part neutrals to form, carboxyl and conjugated double bond are the main functional group in the resinous acid to rosin.Chemical modification through carboxyl and conjugated double bond has been synthesized deep processed products such as nilox resin, staybelite, maleated rosin, acrylic acid rosin and various rosin esters; Comprise also that wherein some can carry out the monomer (CN101215445 of radical polymerization; CN101492591; CN101265392, CN101066918).As follows:
DAE DAME DAB ?DAA DAMA
In the conventional radical polymerization system, chain transfer reaction is irreversible, causes the polymerization degree to reduce, and molecular weight and molecular structure are uncontrollable.Reversible addition-fracture chain transfer polymerization (Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT)) is a kind of important method of activity/controllable free-radical polymerisation (CRP), and it has advantages such as suitable monomer scope is wide.Except common monomer, vinylformic acid, to protic monomers such as vinylbenzenesulfonic acid sodium, Rocryl 400, methylacrylic acid amido ethyl ester or acid, all polymerizations smoothly of alkaline monomer, but also be not used in the polymerization of rosin based material.
The RAFT reaction is mainly by monomer, and contrary addition-fracture chain transfer agents (RAFT reagent) and initiator are formed.RAFT reagent has dithiobenzoic acid isopropylbenzene ester (CDB), dithio benzyl benzoate (BDTB), two thio phenyl acetate isopropylbenzene esters (CPDA), dithiobenzoic acid-1-ethoxycarbonyl-n-propyl (EPDTB), dibenzyl trithiocarbonate (DBTTC), S, S '-two (ɑ-acetophenone) trithiocarbonate (DNTTC) etc.Initiator has Diisopropyl azodicarboxylate, Lucidol, Ammonium Persulfate 98.5, Potassium Persulphate etc.
CDB BDTB CPDA EPDTB
DBTTC BMTTC
Rosin based monomer and conventional esters of acrylic acid or vinyl monomer relatively, one three luxuriant and rich with fragrance structure of ring on the molecular structure has certain sterically hinderedly, influences the structure control property of rosin based monomer in controllable polymerization.Therefore in the selection to RAFT reagent, the control of temperature of reaction is the difficult point and the gordian technique of the regular rosinyl polymkeric substance of preparation.
Summary of the invention
In order to prepare regular type rosin polymer, the invention discloses a kind of preparation method of rosinyl regular polymer, adopt the RAFT polymerization methods to prepare regular type rosin polymer, be rosiny deep processing and utilization based theoretical.
Technical scheme of the present invention is: a kind of preparation method of rosinyl regular polymer; With the rosinyl monomer; Radical polymerization share initiator, reversible addition-fracture chain transfer agents is dissolved in the solvent in certain molar mass ratio, and logical nitrogen removal oxygen, 50 ~ 120
oBehind C reaction 1 ~ 24 h, polymkeric substance is precipitated in methyl alcohol, the rosinyl polymkeric substance that filter then, drying obtains different molecular weight, described rosinyl monomer is for carrying out the rosin derivative of Raolical polymerizable.Can obtain the rosinyl regular polymer of different molecular weight and MWD (PDI) through present method.
Said rosinyl monomer is the Abietyl modified compound that contains propenoate, methacrylic ester, vinyl, allyl group or methyl alkenyl-functional groups;
It is Diisopropyl azodicarboxylate, Lucidol, Ammonium Persulfate 98.5 that said radical polymerization share initiator, and the free crowd that Potassium Persulphate etc. are commonly used draws a kind of in the agent.
Described reversible addition-fracture chain transfer agents (RAFT reagent) is dithiobenzoic acid isopropylbenzene ester (CDB), dithio benzyl benzoate (BDTB), two thio phenyl acetate isopropylbenzene esters (CPDA), dithiobenzoic acid-1-ethoxycarbonyl-n-propyl (EPDTB), dibenzyl trithiocarbonate (DBTTC), S, S '-two (ɑ-acetophenone) trithiocarbonate (DNTTC) etc.
Described rosinyl monomer, reversible addition-fracture chain transfer agents and radical polymerization share initiator according to mol ratio rosinyl monomer: RAFT: radical polymerization share initiator=(2000 ~ 20): 1: the ratio of (1 ~ 0.1) is used.
Described solvent is THF or toluene.
Beneficial effect:
(1) the molecular weight size of rosinyl polymkeric substance is determined by transformation efficiency, and molecular weight is along with the monomeric transformation efficiency of rosinyl presents linear growth;
(2) molecular weight of loose basic based polyalcohol can be regulated with final monomer conversion through the ratio of control monomer and RAFT reagent;
(3) loose basic based polyalcohol can be used as macromole evocating agent, through the synthetic rosin functional type block polymer of RAFT reaction; Being one type of hydrophobic prepolymer with ordered structure, is macromole RAFT reagent with the rosin prepolymer, once more through the RAFT mode, can carry out the structure design of amphiphilic cpds.
(4) for the monomer RAFT polymerization of DAME, with toluene as solvent, at low temperature (78 ~ 80
oC) under, the polymer architecture ratio is better.
Description of drawings
Fig. 1 is embodiment 1 a rosinyl monomer DAME regular polymer
1H NMR figure.
Fig. 2 is the kinetic curve of rosinyl monomer DAME polymkeric substance among the embodiment 1.
Fig. 3 is a rosinyl monomer DAME polymer kinetics GPC curve among the embodiment 1.
Fig. 4 is a rosinyl monomer DAME polymkeric substance GPC curve among the embodiment 2
Fig. 5 is the kinetic curve of rosinyl monomer DAME polymkeric substance among the embodiment 2.
Fig. 6 is the kinetic curve of rosinyl monomer DAME polymkeric substance among the embodiment 3.
Fig. 7 is embodiment 5 rosinyl monomer DAE regular polymers
1H NMR figure.
Fig. 8 is embodiment 6 rosinyl monomer DAB regular polymers
1H NMR figure.
Fig. 9 is embodiment 1 rosinyl monomer DAME regular polymer contact angle figure.
Figure 10 is embodiment 5 rosinyl monomer DAE regular polymer contact angle figure.
Embodiment
Spy of the present invention illustrates it for better implement, but is not limitation of the present invention.
Employed RAFT reagent is self-control among the present invention, prepares with reference to following document: (1) Xiuqiang Xin, Yanmei Wang; Wei Liu; Synthesis of zwitterionic block copolymers via RAFT polymerization. European Polymer Journal, Volume 41, and Issue 7; July 2005, Pages 1539-1545; (2) Andr é J.P. van Zyl, Rutger F.P. Bosch, James B. McLeary; Ronald D. Sanderson, Bert Klumperman. Sythesis of styrene based liquid-filled polymeric nanocapsules by the use of RAFT-mediated polymerization in miniemulsion. Polymer, Volume 46; Issue 11,11 May 2005, Pages 3607-3615. (3) Adam E. Smith; Xuewei Xu; Charles L. McCormick. Stimuli-responsive amphiphilic (co) polymers via RAFT polymerization. Progress in Polymer Science, Volume 35, Issues 1-2; January-February 2010, Pages 45-93.
With DAME monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 66 mg and AIBN (Diisopropyl azodicarboxylate) 4.0 mg; Example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 70 ° of C the reaction 24 hours after, monomer conversion 95 %.Polymericular weight:
M n(GPC): 25600 g/mol, PDI=1.22. Mn (NMR): 37800 g/mol.
With DAME monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 66 mg and AIBN (Diisopropyl azodicarboxylate) 4.0 mg; Example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 100 ° of C the reaction 12 hours after, monomer conversion 35 %.Polymericular weight:
M n(GPC): 10,600 g/mol, PDI=1.29.
M n(NMR): 12900 g/mol.
React after 24 hours monomer conversion 45 %.Polymericular weight:
M n(GPC): 15,300 g/mol, PDI=1.67.
M n(NMR): 17900 g/mol.
Can find out that from reaction,, be reflected at transformation efficiency and be lower than for 35% time 100 ° of C reactions as solvent with toluene, polymerization process is controlled, when transformation efficiency continuation rising, PDI raises, and it is uncontrollable that structure becomes.
With DAME monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 66 mg and AIBN (Diisopropyl azodicarboxylate) 4.0 mg; Example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml THFs, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.After 12 hours polymkeric substance is precipitated the rosinyl polymkeric substance that filter then, drying obtains different molecular weight, monomer conversion 42 % then in methyl alcohol in reaction under 80 ° of C.Polymericular weight:
M n(GPC): 8600 g/mol, PDI=1.46.
M n(NMR): 17000 g/mol
With DAME monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 66 mg and AIBN (Diisopropyl azodicarboxylate) 4.0 mg; Example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml THFs, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 80 ° of C the reaction 24 hours after, monomer conversion 80 %.Polymericular weight:
M n(GPC): 23000 g/mol, PDI=1.82. Mn (NMR): 31800 g/mol.
With DAE monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 68.3 mg and AIBN (Diisopropyl azodicarboxylate) 4.1 mg; Example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 80 ° of C the reaction 23 hours after, monomer conversion 88 %.Polymericular weight:
M n(GPC): 29,100 g/mol, PDI=1.3.
M n(NMR): 35000 g/mol.
With DAB monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 63.8 mg and AIBN (Diisopropyl azodicarboxylate) 3.85 mg; Example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 70 ° of C the reaction 24 hours after, monomer conversion 73 %.Polymericular weight:
M n(GPC): 7100 g/mol, PDI=1.46.
M n(NMR): 31000 g/mol.
With DAA monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 80.0 mg and AIBN (Diisopropyl azodicarboxylate) 4.82 mg; Example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 70 ° of C the reaction 24 hours after, monomer conversion 51 %.Polymericular weight:
M n(GPC): 6100 g/mol, PDI=1.52.
M n(NMR): 17300 g/mol.
With DAMA monomer 10 g; RAFT reagent (CDB; Dithiobenzoic acid isopropyl benzene ester) 76.8 mg and AIBN (Diisopropyl azodicarboxylate) 4.64 mg; Example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 70 ° of C the reaction 24 hours after, monomer conversion 57 %.Polymericular weight:
M n(GPC): 6100 g/mol, PDI=1.47.
M n(NMR): 20300 g/mol.
Embodiment 9
With DAE monomer 10 g; RAFT reagent (BDTB; Dithio benzyl benzoate) 61.3 mg and AIBN (Diisopropyl azodicarboxylate) 4.12 mg; Example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 70 ° of C the reaction 24 hours after, monomer conversion 86 %.Polymericular weight:
M n(GPC): 19100 g/mol, PDI=1.39.
M n(NMR): 34200 g/mol.
Embodiment 10
With DAE monomer 10 g; RAFT reagent (CPDA; Dithio toluylic acid isopropyl benzene ester) 71.8 mg and AIBN (Diisopropyl azodicarboxylate) 4.12 mg; Example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 70 ° of C the reaction 24 hours after, monomer conversion 91 %.Polymericular weight:
M n(GPC): 22600 g/mol, PDI=1.47.
M n(NMR): 36200 g/mol.
Embodiment 11
With DAE monomer 10 g; RAFT reagent (EPDTB; Dithiobenzoic acid-1-ethoxycarbonyl-n-propyl) 70.8 mg and AIBN (Diisopropyl azodicarboxylate) 4.12 mg; Example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene, will dissolve and forward in the eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes in molar ratio.Then under 70 ° of C the reaction 24 hours after, monomer conversion 87 %.Polymericular weight:
M n(GPC): 18600 g/mol, PDI=1.53.
M n(NMR): 34600 g/mol.
With DAE monomer 10 g; RAFT reagent (DBTTC; The dibenzyl trithiocarbonate), 72.8 mg and AIBN (azodiisobutyronitrile) 4.12 mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene in molar ratio; To dissolve and forward in the eggplant type reaction bulb nitrogen bubble deoxygenation 15 minutes to.Then under 70 ° of C the reaction 24 hours after, monomer conversion 83 %.Polymericular weight:
M n(GPC): 16700 g/mol, PDI=1.62.
M n(NMR): 33000 g/mol.
With DAE monomer 10 g; RAFT reagent (DBTTC; The dibenzyl trithiocarbonate), 86.9 mg and AIBN (azodiisobutyronitrile) 4.12 mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) add in the 20 ml toluene in molar ratio; To dissolve and forward in the eggplant type reaction bulb nitrogen bubble deoxygenation 15 minutes to.Then under 70 ° of C the reaction 24 hours after, monomer conversion 80 %.Polymericular weight:
M n(GPC): 14700 g/mol, PDI=1.58.
M n(NMR): 31800 g/mol.
With the solvent of water, the rosinyl regularity matrix material of embodiment 1, embodiment 5 and embodiment 6 is carried out the contact angle test, experimental result shows that all greater than 90 degree, this shows that rosinyl regularity matrix material has better hydrophobic to all contact angle numerical value.
Spectrum analysis
Fig. 1 is embodiment 1 a rosinyl monomer DAME regular polymer
1H NMR figure is that 5.0 ppm do not contain monomer in the proton peak explanation polymkeric substance that does not have vinyl between 6.5 ppm in chemical shift;
The kinetic curve of rosinyl monomer DAME polymkeric substance among Fig. 2 embodiment 1.Kinetic curve is linear, shows that this reaction is a living polymerization;
Rosinyl monomer DAME polymer kinetics GPC curve among Fig. 3 embodiment 1, the GPC curve shows the prolongation along with the reaction times, and monomeric transformation efficiency increases, and molecular weight increases.
Among Fig. 4 embodiment 2, rosinyl monomer DAME reacts 12 hours post polymerization thing GPC curves under 100 ° of C, and molecular weight does
M n(GPC): 10,600 g/mol, PDI=1.29;
Fig. 5 is the kinetic curve that rosinyl monomer DAME reacts under 100 ° of C among the embodiment 2, from dynamics research show have only when reaction conversion ratio be active reaction in 35% this polyreaction when following, reaction process is controlled.When reaction conversion ratio was higher than 35%, transformation efficiency was almost constant, that is to say that polyreaction stops.
Fig. 6 is the kinetic curve that rosinyl monomer DAME reacts under 80 ° of C among the embodiment 3.Kinetic curve shows that polymerization rate improves; Reaction simultaneously begins slower; Comparison diagram 2 and Fig. 6, the kinetic curve linear relationship of under 70 ° of C, reacting among Fig. 2 is better, and this shows that the polyreaction of MAEDA is more suitable under relatively low temperature, carrying out.
Fig. 7 is embodiment 5 rosinyl monomer DAME regular polymers
1H NMR figure is that 5.0 ppm do not contain monomer in the proton peak explanation polymkeric substance that does not have vinyl between 6.5 ppm in chemical shift;
Fig. 8 is embodiment 6 rosinyl monomer DAB regular polymers
1H NMR figure is that 5.0 ppm do not contain monomer in the proton peak explanation polymkeric substance that does not have vinyl between 6.5 ppm in chemical shift.
Contact angle numerical value among Fig. 8, Fig. 9 and Figure 10 is more than 90 degree; The rosinyl polymkeric substance that showed the preparation of RAFT polymerization is one type of hydrophobic prepolymer with ordered structure; It can make macromole RAFT reagent, and another segment polymer of grafting is realized the design of molecular structure.
Claims (6)
1. the preparation method of a rosinyl regular polymer; It is characterized in that; With rosinyl monomer, radical polymerization share initiator, reversible addition-fracture chain transfer agents is dissolved in the solvent, and logical nitrogen removes oxygen, behind 50 ~ 120 ℃ of reaction 1 ~ 24 h; Polymkeric substance is precipitated the rosinyl polymkeric substance that filter then, drying obtains different molecular weight in methyl alcohol; Described rosinyl monomer is for carrying out the rosin derivative of Raolical polymerizable.
2. the preparation method of rosinyl regular polymer as claimed in claim 1 is characterized in that, described rosinyl monomer is the Abietyl modified compound that contains propenoate, methacrylic ester, vinyl, allyl group or methyl alkenyl-functional groups.
3. the preparation method of rosinyl regular polymer as claimed in claim 1 is characterized in that, it is Diisopropyl azodicarboxylate, Lucidol, Ammonium Persulfate 98.5 that described radical polymerization share initiator, a kind of in the Potassium Persulphate.
4. the preparation method of abietyl regular polymer as claimed in claim 1; It is characterized in that; Described reversible addition-fracture chain transfer agents is dithiobenzoic acid isopropylbenzene ester, dithio benzyl benzoate, two thio phenyl acetate isopropylbenzene esters, dithiobenzoic acid-1-ethoxycarbonyl-n-propyl, dibenzyl trithiocarbonate, S, a kind of in S '-two (ɑ-acetophenone) trithiocarbonate.
5. the preparation method of rosinyl regular polymer as claimed in claim 1; It is characterized in that described rosinyl monomer, reversible addition-fracture chain transfer agents and radical polymerization share initiator according to mol ratio rosinyl monomer: reversible addition-fracture chain transfer agents: radical polymerization share initiator=(2000 ~ 20): 1: the ratio of (1 ~ 0.1) is used.
6. the preparation method of rosinyl regular polymer as claimed in claim 1 is characterized in that, described solvent is THF or toluene.
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| CN108070061A (en) * | 2016-11-15 | 2018-05-25 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of rosin and its derivative group block copolymer miniemulsion |
| CN110790905A (en) * | 2019-11-06 | 2020-02-14 | 河北工业大学 | Novel organic two-dimensional material and preparation method thereof |
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| CN108070061A (en) * | 2016-11-15 | 2018-05-25 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of rosin and its derivative group block copolymer miniemulsion |
| CN110790905A (en) * | 2019-11-06 | 2020-02-14 | 河北工业大学 | Novel organic two-dimensional material and preparation method thereof |
| CN110790905B (en) * | 2019-11-06 | 2021-12-24 | 河北工业大学 | Organic two-dimensional material and preparation method thereof |
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