CN102321198A - Method for preparing bimodal distribution polymer - Google Patents
Method for preparing bimodal distribution polymer Download PDFInfo
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- CN102321198A CN102321198A CN201110177187A CN201110177187A CN102321198A CN 102321198 A CN102321198 A CN 102321198A CN 201110177187 A CN201110177187 A CN 201110177187A CN 201110177187 A CN201110177187 A CN 201110177187A CN 102321198 A CN102321198 A CN 102321198A
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Abstract
The method discloses a method for preparing a bimodal distribution polymer. The method comprises the following steps of preparing a polymerization system, performing an RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction at 50-90 DEG C for at least one hour, separating and purifying, and obtaining the bimodal distribution polymer, wherein the polymerization system comprises a monomer, a free radical initiating agent, a single head RAFT reagent and a double head RAFT reagent; the free radical initiating agent is one selected from styrene, acrylic, water soluble N-isopropyl acrylamide and the like; the conventional free radical initiating agent is one selected from azobisisobutyronitrile and benzoyl peroxide; and the single and double functional-group RAFT reagent combination is one selected from dithiocarbamate and trithiocarbonates. According to the invention, the bimodal distribution polymer with molecular weights and controllable molecular weight distribution can be synthesized because the used RAFT method has 'active'/controllable polymerization characteristics.
Description
Technical field
The present invention relates to the reversible addition of a kind of employing-fracture chain transfer (Reversible Addition-Fragmentation Chain Transfer, RAFT) method of the synthetic bimodal distribution polymkeric substance of polymerization method.
Background technology
The molecular weight of polymkeric substance and molecular weight distributing index have determined its physicals, mechanical property and processing characteristics.The less polymkeric substance of molecular weight has toughness and flowing property preferably, but the rigidity of polymkeric substance can decrease.The polymkeric substance that molecular weight is bigger has mechanical property preferably, but its toughness can corresponding reduction.Even high molecular weight material demonstrates good toughness, but because their high melt viscosity, it is very difficult to make processing get up.For some special application, usually need polymkeric substance to have mechanical property and processing characteristics preferably simultaneously.In order to overcome the shortcoming that use properties and processing characteristics can not have both; Polymkeric substance through synthetic bimodal distribution; HMW and low-molecular-weight polymkeric substance are promptly arranged simultaneously, can be under many extreme conditions balance with optimize Drawing abillity (low molecular weight part) and use properties (HMW part).Under processing temperature, low molecular weight part can improve the flowability of polymer materials in the polymkeric substance; Under use temperature, the HMW part can improve the use properties of material in the polymkeric substance.The preparation method of bimodal distribution polymkeric substance generally includes following several kinds:
(1) physical blending, this method are after synthesizing the polymkeric substance of high and low relative molecular mass respectively, again both are mixed (referring to: Xue Feng, Ma Guangsheng. broad peak or two sections polymerization polyvinyl resins of bimodal distribution performance study.
The modern plastics processed and applied,
2007, 19,13-16.)
(2) two-step reaction, its method are meant under a kind of polymerizing condition synthetic earlier wherein a kind of polymkeric substance of relative molecular mass, in the reaction of second step, change then the polymkeric substance that reaction conditions obtains another kind of relative molecular mass (referring to:
Abedi,?S.;?Hassanpour,?N.?Preparation?of?Bimodal?Polypropylene?in?Two-Step?Polymerization.?
J.?Appl.?Polym.?Sci.,
2006 ,?101,?1456-1462.）。
(3) use chain-transfer agent or linking agent etc.; The general earlier synthetic low-molecular weight polymer of this method; Synthesize higher molecular weight polymer (referring to Tobita, H. Bimodal Molecular Weight Distribution Formed in the Emulsion Polymerization of Ethylene. in reaction system, adding chain-transfer agent or linking agent then
J. Polym. Sci., Part A:Polym. Chem., 2002, 40,3426-3433.).
(4) make spent mixed catalyst or mixed catalyst system, the compound catalystsystem that nickel and zirconium, titanium are formed after promotor MAO (MAO) activation, can make the single ethylene polymerization prepare the Vilaterm of bimodal pattern long-chain branch.Equally, iron, cobalt, chromium cpd are after using a large amount of MAO activation or use ziegler natta catalyst, and the Vilaterm that also can prepare bimodal distribution is (referring to (a) Li, L.; Wang, Q. Synthesis of Polyethylene with Bimodal Molecular Weight Distribution by Supported Iron-Based Catalyst.
J. Polym. Sci., Part A:Polym. Chem.,
2004, 42,5662-5669. (b) Yamamoto, K.; Ishihama, Y.; Sakata, K. Preparation of Bimodal HDPEs with Metallocene on Cr-Montmorillonite Support
. J. Polym. Sci. Part A:Polym. Chem.,
2010, 48,3722-3728.).
Though these methods can successfully be synthesized the polymkeric substance of bimodal distribution, the two-step reaction method complicated operation contains toxic metal in the mixed catalyst law system, and process for synthetic catalyst is complicated, costs an arm and a leg.The most important thing is that above several method is difficult to synthetic molecular weight and the simultaneously controlled bimodal polymers of MWD.
Reversible Addition-Fragmentation Chain Transfer (RAFT; Being reversible addition-fracture chain transfer) polymerization method is as one of " activity "/controllable free radical polymerization process of tool potentiality, and it is proposed in 1998 years by people such as Rizzardo first.The RAFT polymerization is exactly in the radical polymerization system of routine, to add suitable R AFT reagent, and used monomer, initiator, solvent and temperature of reaction are all consistent with conventional radical polymerization.Therefore it is the same with common radical polymerization, has to operate and aftertreatment is simple, the diversified advantage of polymerization methods, is one of " activity "/controllable free radical polymerization process of tool industrial prospect.From present existing report, still do not use the bibliographical information of the synthetic bimodal distribution polymkeric substance of RAFT method.
Summary of the invention
Goal of the invention of the present invention provides a kind of method for preparing the bimodal distribution polymkeric substance.
For reaching the foregoing invention purpose; The technical scheme that the present invention adopts is: a kind of method for preparing the bimodal distribution polymkeric substance may further comprise the steps: the preparation polymerization system, carried out the RAFT polyreaction at least 1 hour under 50～90 ℃; Separate and purify, obtain the bimodal distribution polymkeric substance;
Said polymerization system comprises monomer, radical initiator, single head RAFT reagent, double end RAFT reagent; Wherein, n (monomer) ﹕ n (initiator) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200 ~ 100000 ﹕ 1～30 ﹕ 1～150 ﹕ 1～150;
Wherein, said monomer is the monomer of free redical polymerization, is selected from: vinylbenzene, esters of acrylic acid, water miscible
NA kind of in the-NSC 11448 etc.; Said esters of acrylic acid is preferably: methyl acrylate, ethyl propenoate, propyl acrylate, Bing Xisuandingzhi, TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate or NSC 20956;
Said initiator is the conventional free radical initiator, is selected from: a kind of in Diisopropyl azodicarboxylate (AIBN), the BPO (BPO);
Said single head RAFT agent is selected from: dithiocarbamates
or trithiocarbonate esters
in one;
The double-headed RAFT agent is selected from: dithiocarbamates
or trithiocarbonate esters
in one;
Wherein R, R
1, R
2Be selected from separately :-Ph ,-Ph-OCH
3,-(CH
3)
2A kind of in alkyl, naphthylene group or the carbazole group of C-C ≡ N, C1～C4; R
3Be selected from
,
,
Or
In a kind of, n=7～23 wherein.
In the technique scheme, can be through the molecular weight of adjustment reaction times controlling polymers.
In the technique scheme, can come the massfraction of high and low polydispersity polymer in the controlling polymers through the molar ratio of adjusting single, double RAFT reagent.For example need obtain the high-molecular weight polymer of more ratios, can realize through the ratio that increases double end RAFT reagent, on the contrary then opposite.
In the technique scheme, the narrow molecular weight distribution of resulting polymers (PDI 1.2), the actual molecular weight of resulting polymers conforms to theoretical molecular.
In the technique scheme, said RAFT polyreaction can be carried out polymerization with body or solution polymerization mode.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the present invention proposes to use the synthetic bimodal distribution polymkeric substance of method of " activity "/controllable free-radical polymerisation first; And the molecular weight of two kinds of polymkeric substance and MWD are simultaneously controlled, for molecular level blended bimodal distribution macromolecular material provides a kind of novel method.
2. because the present invention has adopted the RAFT polymerization method; Have the polymerization single polymerization monomer face width, polymerization methods is various and simple to operate; Do not need complicated last handling process, stable in the air and this reaction of the used chemical reagent of the present invention can be operated under air atmosphere, is convenient to suitability for industrialized production.
3. because in the polymerization system of the present invention, the adjustable ratio of single, double RAFT reagent can be synthesized the adjustable bimodal polymers of massfraction of high and low molecular weight.
4. because the present invention has adopted the RAFT polymerization system, and the molecular weight of resulting polymers can design easily, and polymer terminal group still has activity, can be used to the more synthetic activity/controlled block with topological framework, graft copolymer.
Description of drawings
Fig. 1 is reaction kinetics figure (1a) and the transformation efficiency and the molecular weight graph of a relation (1b) of the synthetic bimodal distribution polymkeric substance of single, double RAFT agent combination of dithiocarbamate among the embodiment one;
Fig. 2 is the nuclear-magnetism figure of bimodal distribution polymkeric substance among the embodiment four;
Fig. 3 is reaction kinetics figure (3a) and the transformation efficiency and the molecular weight graph of a relation (3b) of the synthetic bimodal distribution polymkeric substance of single, double RAFT agent combination of trithiocarbonate class among the embodiment five.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Used chemical reagent among the embodiment: vinylbenzene (St), 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Carbazole, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Diisopropyl azodicarboxylate (AIBN), 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Resorcinol, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Dithiocarbonic anhydride, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Methyl-sulphoxide, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; THF (THF), methylene dichloride and methyl alcohol, analytical pure, Changshu City Yang Yuan chemical reagent ltd; Triethylamine, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Benzyl sulfhydrate, propylmercaptan, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; 1,4-chloromethylbenzene, cylite, 99%, China Medicine (Group) Shanghai Chemical Reagent Co..
Testing tool and condition:
Gel permeation chromatograph: the 1515 type GPC of U.S. Waters (Waters); Condition determination: HR1, HR3 and the series connection of HR4 three posts are used, the differential detector, moving phase is THF (1mL/min), 30 ℃ of column temperatures are done correction with polymethylmethacrylate or polystyrene standards.
NMR: 400 megahertzes; Condition determination: with CDCl
3Being solvent, is internal standard substance with the TMS, and probe temperature is a room temperature.
Embodiment one: with the synthetic bimodal distribution PS (PS) of the dithiocarbamate RAFT of the single, double functional group agent combination that waits molar ratio
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200～2000 ﹕ 1 ﹕ 1 ~ 20 ﹕ 1 ~ 10; Add single head RAFT reagent successively; Double end RAFT reagent, AIBN, St is in the ampoule of 5 mL; After feeding 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react the ampoule behind the tube sealing by preset time.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the THF dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, suction filtration, washing, oven dry can obtain the PS of " activity " after the placement of spending the night;
Wherein, representational single head RAFT agent structure does in the dithiocarbamate
Representational bifunctional RAFT agent structure is in the dithiocarbamate:
Fig. 1 is the reaction kinetics figure of the synthetic bimodal distribution polymkeric substance of RAFT method; Polymerizing condition is: St=3mL, [St]
0/ [AIBN]
0/ [single head RAFT reagent]
0/ [double end RAFT reagent]
0=1200:1:2.5:2.5, T=75 ℃, anaerobic.Can be known by Fig. 2 a and Fig. 2 b: the concentration of the radical of deriving in the reaction process keeps constant, and high and low polydispersity polymer conforms to its corresponding theory molecular weight, and MWD is narrower.High and low polydispersity polymer is the linear growth along with the growth of polymerization time all, and polymerization process is the molecular weight of controlling polymers preferably.Simultaneously also can find out no matter be the polymkeric substance that under high and low monomer conversion condition, all can obtain bimodal distribution.
Embodiment two: single, double RAFT agent combination of the dithiocarbamate under the different mol ratio example (the RAFT reagent type is with embodiment one) synthesized bimodal distribution PS (PS)
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200 ~ 10000 ﹕ 1 ~ 30 ﹕ 1 ~ 150 ﹕ 150 ~ 1; Add single head RAFT reagent successively; Double end RAFT reagent, AIBN, St is in the ampoule of 5 mL; After feeding 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react the ampoule behind the tube sealing by preset time.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the THF dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, suction filtration, washing, oven dry can obtain the PS of " activity " after the placement of spending the night.
The data of embodiment two are seen table 1.
The result
of the synthetic bimodal distribution PS of single, double RAFT agent combination of table 1. different mol ratio example
Reaction conditions: 3.0 mL vinylbenzene, mass polymerization, 75 ℃ of temperature of reaction.
A)R=[St]
0/ [AIBN]
0/ [single head RAFT reagent]
0/ [double end RAFT reagent]
0
B)Low-molecular weight polymer/high-molecular weight polymer;
M N, thBe the molecular weight that Theoretical Calculation draws, the molecular weight of low-molecular weight polymer=([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, single head RAFT reagent, high-molecular weight polymer molecular weight=2 * ([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, double end RAFT reagent M N, GPCTest the molecular weight that draws for gel permeation chromatography (GPC);
C)Low-molecular weight polymer/high-molecular weight polymer;
M w/
M nTest the molecular weight distributing index that draws for gel permeation chromatography (GPC).
Can find out that by data in the table 1 when in system, adding the single, double RAFT of the functional group reagent of different mol ratio example, reaction still is controlled.Like single head RAFT reagent: during double end RAFT reagent=1:100, still can obtain the bimodal distribution polymkeric substance, reaction system PDI is still very low.
Embodiment three: the bimodal distribution PS of single, double RAFT agent combination of dithiocarbamate (the RAFT reagent type is with embodiment one) synthetic macromolecule amount.
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=10000 ~ 100000 ﹕ 1 ﹕ 2～10 ﹕ 2～10; Add single head RAFT reagent successively; Double end RAFT reagent, AIBN, St is in the ampoule of 5 mL; After feeding 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react the ampoule behind the tube sealing by preset time.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the THF dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, suction filtration, washing, oven dry can obtain the PS of " activity " after the placement of spending the night.
The data of embodiment three are seen table 2.
The polymerization result of table 2. synthetic macromolecule amount bimodal polystyrene
Reaction conditions: 12.0 mL vinylbenzene, mass polymerization, 75 ℃ of temperature of reaction.
A)R=[St]
0/ [AIBN]
0/ [single head RAFT reagent]
0/ [double end RAFT reagent]
0
B)Low-molecular weight polymer/high-molecular weight polymer;
M N, thBe the molecular weight that Theoretical Calculation draws, the molecular weight of low-molecular weight polymer=([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, single head RAFT reagent, high-molecular weight polymer molecular weight=2 * ([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, double end RAFT reagent M N, GPCTest the molecular weight that draws for gel permeation chromatography (GPC);
C)Low-molecular weight polymer/high-molecular weight polymer;
M W/ M nTest the molecular weight distributing index that draws for gel permeation chromatography (GPC).
Can be found out that by data in the table 2 when using the bimodal polymers of RAFT method synthetic macromolecule amount, when molecular weight was higher, reaction still was controlled, reaction system PDI is still very low.
Embodiment four: the nuclear magnetic spectrogram of the synthetic bimodal distribution PS of single, double RAFT agent combination of dithiocarbamate (the RAFT reagent type is with embodiment one).
In living polymerization, the nuclear magnetic spectrogram of polymkeric substance is used for the end group of polymkeric substance is analyzed, with the living polymerization characteristic of checking polymkeric substance.
Carry out the nuclear-magnetism test of PS according to well known to a person skilled in the art experimental procedure.Test result such as Fig. 2 show that the end of bimodal distribution polymkeric substance has RAFT reagent group.
Embodiment five: with the synthetic bimodal distribution PS (PS) of the trithiocarbonate class RAFT of the single, double functional group agent combination that waits molar ratio
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200～2000 ﹕ 1 ﹕ 1 ~ 20 ﹕ 1 ~ 10; Add single head RAFT reagent successively; Double end RAFT reagent, AIBN, St is in the ampoule of 5 mL; After feeding 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react the ampoule behind the tube sealing by preset time.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the THF dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, suction filtration, washing, oven dry can obtain the PS of " activity " after the placement of spending the night;
Wherein, representational simple function group RAFT agent structure is in the trithiocarbonate class:
Representational bifunctional RAFT agent structure is in the trithiocarbonate class:
.
Fig. 3 is the ln ([M] of 75 ℃ of following RAFT method polymerization St
0/ [M])-the time dynamics curve.Be illustrated as the first order kinetics of monomer concentration, show that the number of free radical of deriving is a constant in polymerization process.Simultaneously, also can be observed inductive phase (≈ 7.5 h) among Fig. 3 a.According to RAFT polymerization-filling mechanism, reaction AIBN in early stage decomposes the radical that produces and possibly combine with trithiocarbonate RAFT reagent, and the midbody rate of decomposition of formation is slower, thereby the inductive phase of a very long time occurs.But along with the carrying out of reaction, derive in the system radical and RAFT reagent are finally set up a reversible running balance.The molecular weight that from Fig. 3 b, can also significantly find out polymkeric substance increases along with monomer conversion is linear, and the PS of preparation still have narrower molecular weight distributing index (
M w/
M n) (<1.4).Molecular weight obtains theoretical molecular with mol ratio calculating according to the initial concentration of St and RAFT reagent and is close.More than these all show and use single, double trithiocarbonate class RAFT reagent can synthesize the bimodal distribution polymkeric substance.
Claims (3)
1. a method for preparing the bimodal distribution polymkeric substance is characterized in that, may further comprise the steps: the preparation polymerization system, under 50～90 ℃, carried out the RAFT polyreaction at least 1 hour, and separate and purify, obtain the bimodal distribution polymkeric substance;
Said polymerization system comprises monomer, radical initiator, single head RAFT reagent, double end RAFT reagent; Wherein, n (monomer) ﹕ n (initiator) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200 ~ 100000 ﹕ 1～30 ﹕ 1～150 ﹕ 1～150;
Wherein, said monomer is the monomer of free redical polymerization, and said initiator is the conventional free radical initiator;
Said single head RAFT agent is selected from: dithiocarbamates
or trithiocarbonate esters
in one;
The double-headed RAFT agent is selected from: dithiocarbamates
or trithiocarbonate esters
in one;
Wherein R, R
1, R
2Be selected from separately :-Ph ,-Ph-OCH
3,-(CH
3)
2A kind of in alkyl, naphthylene group or the carbazole group of C-C ≡ N, C1～C4; R
3Be selected from
,
,
Or
In a kind of, n=7～23 wherein.
2. according to the said method for preparing the bimodal distribution polymkeric substance of claim 1, it is characterized in that said monomer is selected from: vinylbenzene, esters of acrylic acid, water miscible
NA kind of in the-NSC 11448.
3. according to the said method for preparing the bimodal distribution polymkeric substance of claim 1, it is characterized in that said initiator is the conventional free radical initiator, is selected from: a kind of in Diisopropyl azodicarboxylate, the BPO.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105555855A (en) * | 2013-09-20 | 2016-05-04 | 3M创新有限公司 | Trithiocarbonate-containing addition-fragmentation agents |
| CN110606902A (en) * | 2019-07-29 | 2019-12-24 | 长兴电子（苏州）有限公司 | Novel macromolecular photoinitiator and synthesis method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020729A (en) * | 2007-03-26 | 2007-08-22 | 浙江大学 | Process of preparing polybutyl acrylate with narrow molecular weight distribution |
| CN102083863A (en) * | 2008-03-07 | 2011-06-01 | 卡内基梅隆大学 | Improved controlled radical polymerization processes |
-
2011
- 2011-06-28 CN CN 201110177187 patent/CN102321198B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020729A (en) * | 2007-03-26 | 2007-08-22 | 浙江大学 | Process of preparing polybutyl acrylate with narrow molecular weight distribution |
| CN102083863A (en) * | 2008-03-07 | 2011-06-01 | 卡内基梅隆大学 | Improved controlled radical polymerization processes |
Non-Patent Citations (1)
| Title |
|---|
| 朱健等: "硫代羰基化合物中Z和R基团结构对苯乙烯RAFT聚合的影响", 《中国科技论文在线》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105555855A (en) * | 2013-09-20 | 2016-05-04 | 3M创新有限公司 | Trithiocarbonate-containing addition-fragmentation agents |
| CN105555855B (en) * | 2013-09-20 | 2018-08-14 | 3M创新有限公司 | Include addition-clastogen of trithiocarbonate |
| CN110606902A (en) * | 2019-07-29 | 2019-12-24 | 长兴电子（苏州）有限公司 | Novel macromolecular photoinitiator and synthesis method thereof |
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