CN105218715A - A kind of by the assorted thioketones of aromatic ring-shaped sulphur (oxygen) and derivative thereof and radical initiator and active free radical polymerization method - Google Patents
A kind of by the assorted thioketones of aromatic ring-shaped sulphur (oxygen) and derivative thereof and radical initiator and active free radical polymerization method Download PDFInfo
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- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
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- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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Abstract
The invention discloses a kind of by the assorted thioketones of aromatic ring-shaped sulphur (oxygen) and derivative thereof and radical initiator and active free radical polymerization method, use aromatic ring-shaped thioketones (C=S-Ph2 (X)), X is C, N, O, S (using two phenyl ring links) and derivative thereof, as initiation control agent, make vinyl monomer carry out the method for controllable/active free radical polymerization.Feature is by C=S-Ph2 (X) and the conventional radical initiator such as derivative and AIBN thereof and use, can obtain the polymkeric substance of the controlled one end of molecular chain conformation with dormancy group in a heated condition; The polymkeric substance of gained also can be used to cause other monomers as macromole evocating agent and to prepare segmented copolymer.The polymerization process operating procedure that the present invention adopts is simple, and monomer is applied widely, and can be applicable in the polymerization processs such as the thermopolymerization of body, solution, emulsion and suspension etc., the industrial applications for living free radical polymerization creates good basis.
Description
Technical field
The present invention relates to use one class to come from the mix initiation control agent of thione structure and derivative thereof of X and prepare the method for living-radical polymers, and use this living-radical polymers to prepare the method for segmented copolymer as macromole evocating agent.
Background technology
Molecular weight and the controlled polymer materials of molecular weight distribution are in such as polymer crystallization, self-assembly field, the synthesis and preparation field of type material, field of surface modification, and biomedicine field has a wide range of applications, therefore, the very big concern that the controlled polymer materials of molecular chain conformation causes science and industry member is prepared.At present, existing much about the research work of living polymerization, comprise active anionic polymerization, living cationic polymerization, living coordination polymerization, active ring-opening polymerization and active free radical polymerization.Wherein active free radical polymerization possesses simple to operate, is applicable to the advantages such as various of monomer, becomes rapidly popular research direction.Since nineteen eighty-two, invent multiple main active free radical polymerization method successively, comprise thermal initiation-transfer-cessation method (Iniferter) (Makromol.Chem.RapidCommun., 1982,3,133; ), stabilizing active radical polymerization (SFRP) (Macromolecular, 1993,26,2987), atom transfer radical polymerization (ATRP) (J.Am.Chem.Soc., 1995,117,5614) and reversible addition and fragmentation chain transfer (RAFT) polymerization (Macromolecular, 1998,31,5559) etc.Existing many research reports these four kinds of polymerization systems and is preparing advantage and the application of molecular weight and the controlled polymkeric substance of molecular weight distribution, but these four kinds of systems still come with some shortcomings separately, such as Iniferter polymerization process is not fine to the control of polymerization process, make the molecular weight of resulting polymers and theoretical value deviation comparatively large, molecular weight distribution index is wider; And SFRP polymerization needs higher polymerization temperature, and most of living free radical polymerization only has controllability to Styrene and its derivatives, although oneself has highly active nitroxyl free radical to be found, building-up process is complicated, and productive rate is low; The disadvantage of ATRP is that transition metal complex does not consume in the course of the polymerization process, be difficult to purify, residual easily cause aging and other side effects of polymkeric substance in the polymer, simultaneously, due to the existence of low price transition metal, make its hope further developed on industrial road very undesirable; The preparation process of the two sulfur ester of the chain-transfer agent needed for RAFT polymerization needs multistep organic synthesis, and usual polymerisate is with the color of two sulfur ester, product has certain bio-toxicity simultaneously, is difficult to be applied in the macromolecular material with direct body contact.1996, Ranby and Yang Wantai found, under UV-irradiation, light trigger benzophenone (BP) can capture the hydrogen of substrate surface, produced surface free radical initiated polymerization, and can with the semipinacol free radical coupling being reduced generation by BP; The reversibly coupling and rupturing in grafted chain end of semipinacol free radical, thus control the growth of grafted chain, achieve controlled active surface graft polymerization (Macromolecules, 1996,29,3308).Subsequently, the research such as poplar and Yin finds the isopropyl thioxanthone (ITX) with similar benzophenone structural, also can produce ITX-semipinacol free radical controls grafted chain growth as active dormancy group under visible light illumination.
On this basis, poplar sends out a kind of novel active polymerization system clear: cyclic aromatic semipinacol group is living polymerization new system (the CMP) (Polym.Chem. causing/cause control agent, 2012,3,1982) patent No. is 102181001A; 102181001B, wherein, cyclic aromatic semipinacol group both can carry out trigger monomer polymerization as initiator, meanwhile, and again can as initiation control agent, with chain free radical addition/fracture, thus the insertion realizing monomer chain linked to owner increases.The method synthesis is simple, not containing metal, and does not have toxicity, has good industrial prospect.But, due to cyclic aromatic semipinacol group itself in the polymerization, easily produce H radical transfer shift reaction, H free radical can cause radical polymerization rapidly, thus make the control of experiment condition need very accurate.Meanwhile, the initiation be coupled together by two cyclic aromatic semipinacol free radicals/initiation control agent itself, to light and heat comparatively responsive, be inconvenient to store.And, from initiator molecule structure, due to the conjugation of cyclic aromatic semipinacol itself and the impact of space steric effect, make the initiating activity of carbon radicals very low, thus it is lower to result in trigger rate in whole polymerization system, whole polyreaction has longer inductive phase.
At the living polymerization TKMP (Chem.Commun. that thioketones regulates, 2006,835) in, two conjugation groups are directly connected with carbon sulphur double bond (C=S), and between Liang Ge conjugation group, do not have chemical bond the two to be linked together, wherein, carbon sulphur double bond (C=S) can with decompose as AIBN ruptures the chain free radical produced by initiator and be coupled/rupture, make monomer can insert chain free radical thus realize the growth of monomer.What use due to this system is not the thioketones of cyclic aromatic structure, but the thioketones of the carbon atom both sides of the carbon sulphur double bond (C=S) of main regulating effect has been connected to by two conjugation groups, make the initiating activity of carbon atom higher, simultaneously, less with chain free radical coupling ability, finally cause, the product that aforesaid method obtains, molecular weight increases not obvious, and molecular weight distribution is very huge.Effect molecular weight and molecular weight distribution being carried out to Effective Regulation can not be played.
In view of above reason, we have designed and synthesized a series of initiation control agent structure, two conjugation groups are directly connected with carbon sulphur double bond (C=S), and by chemical bond, the two is linked together between Liang Ge conjugation group, define the structure of a series of mixed by aromatic ring-shaped X thioketones (C=S-X) and derivative thereof, and this structure is applied in the regulation and control of living polymerization.Therefore, the present invention uses one to comprise aromatic ring-shaped X and to mix the initiation control agent of thioketones (C=S-X), the primary group of free radicals that the homolysis such as the initiator A IBN it be polymerized with conventional free radical produce, and the chain free radical addition/fracture produced in polymerization process, thus realize monomer insertion polymerization owner chain, realize the growth of polymericular weight, and prepare segmented copolymer with the polymkeric substance generated for macromole evocating agent causes other monomers.The living polymerisation process technique that the present invention relates to is simple, and reaction conditions is gentle, and monomer is applied widely, and the initiation control agent of use adopts a step methodology of organic synthesis, the pure and colorless and odorless of the polymkeric substance preparing gained.The living polymerisation process that the present invention relates to can be applied among the four large polymerization processs such as body, solution, emulsion and suspension polymerization, is applicable to suitability for industrialized production.
Summary of the invention
The invention provides one controlled/living polymerisation process efficiently, use a kind of such as formula (1) initiation control agent, it can with traditional radical initiator AIBN etc., realize molecular weight in a heated condition with monomer to increase with the increase of transformation efficiency, reach the object that controls molecular weight and molecualr weight distribution (PDI=Mw/Mn) simultaneously and ensure gained such as formula (2) polymkeric substance, there is initiating activity again, can be used to cause other monomers and prepare segmented copolymer.
Its triggering mechanism is as follows:
Chain causes:
Chainpropagation:
In chain causes, traditional initiator produces two primary group of free radicals as AIBN decomposes, is polymerized by primary group of free radicals trigger monomer, produces chain free radical.
In chainpropagation, to mix the introducing of thioketones owing to causing control agent-aromatic ring-shaped X, aromatic ring-shaped X thioketones of mixing can be coupled with chain free radical, generates one by the stable benzyl position carbon radicals of the large steric group of aromatic ring-shaped X heterocompound formation.This benzyl position carbon radicals both can initiated polymerization, can be coupled with chain free radical/rupture again, make monomer can continue to insert in main chain, realize the growth of molecular weight.Meanwhile, the coupling/fracture of carbon-sulfur bond can make monomer insert in chain free radical equally, realizes the growth of molecular weight, so the growth of molecular weight, is completed jointly by these two portions.
Body series has following features:
1. monomer is applied widely, be applicable to methacrylate-based monomer (as methyl methacrylate), acrylic ester monomer (as methyl acrylate), styrene monomer (as alpha-methyl styrene), vinyl acetate between to for plastic esters monomer (as vinyl acetate), acrylic monomer (as methacrylic acid), olefin monomer (as n-butene), anhydrides monomer (as maleic anhydride), one or more in amides monomer (as acrylamide).
2. go for various polymerization process: as body, solution, emulsion, reversed-phase emulsion, suspension or precipitation heterogeneous polymerization.
3. using obtained above such as formula the polymkeric substance shown in (2) as macromole evocating agent, then add one or more monomers, different polymerization processs can be adopted respectively, all can obtain the chain extension obtaining structure-controllable or block polymer.
A kind of by the assorted thioketones of aromatic ring-shaped sulphur (oxygen) and derivative thereof and radical initiator and active free radical polymerization method, it is characterized in that comprising the following steps:
(1), in the mixture formed at one or more monomers, add such as formula one or more in the initiation control agent shown in (1), form dual initiator polymerization system trigger monomer with all kinds of thermal free radical initiator and react; Causing control agent is that 1:50-50:1 mixes with thermal free radical initiator mol ratio;
In formula (1), R substituent is H, halogen, alkyl, carboxyl, aldehyde radical, cyano group or methoxyl group; R accounts for phenyl ring 1, any one or multiple position of 2,3,4, and X substituting group is C, N, O, S, P;
(2) according to initiation control agent and monomer mole ratio be 1:10-1:100000, thermal free radical initiator and initiator control agent and monomer are together placed in reaction flask, after the degassed or logical nitrogen deoxygenation of sealing freeze thawing, 4-72 hour is reacted under 40-150 degree, obtain the polymkeric substance that molecular weight and molecualr weight distribution is all controlled, shown in (2);
In formula (2), polymerization degree m, n=1-1000, wherein X is the one in C, N, O, P, S; R
1, R
2, R
3, R
4for the different substituents of various monomer.
Further, using obtained above such as formula the polymkeric substance shown in (2) as macromole evocating agent, then add one or more monomers, adopt different polymerization processs respectively, all can obtain the chain extension obtaining structure-controllable or block polymer.
Further, polymerization process is body, solution, emulsion, reversed-phase emulsion, suspension or precipitation heterogeneous polymerization.
Further, described monomer is methacrylate-based monomer, acrylic ester monomer, styrene monomer, vinyl acetate between to for plastic esters monomer, acrylic monomer, olefin monomer, anhydrides monomer, one or more in amides monomer.
Further, described monomer is methyl methacrylate, methyl acrylate, alpha-methyl styrene, vinyl acetate, methacrylic acid, n-butene, maleic anhydride, one or more in acrylamide.
Further, cause control agent and adopt thia thioketones;
The polymkeric substance obtained prepared by described method, shown in (2);
In formula (2), polymerization degree m, n=1-1000, wherein X is the one in C, N, O, P, S; R
1, R
2, R
3, R
4for the different substituents of various monomer.
The preparation of initiator used in the present invention and method of purification:
Lawesson reagent (2.5mmol), thioxanthone or its homologue (4mmol) are put into 50mL toluene, 1-72 hour is reacted under 40-150 degree, add saturated sodium bicarbonate solution afterwards and remove excessive lawesson reagent, separatory, organic phase to be spin-dried for, and with petroleum ether extraction, by product recrystallization three times, cryogenic vacuum is dried, and productive rate is about 80%.Wherein the nuclear magnetic spectrogram of C=S-Ph2 (S) as shown in Figure 1.
According to above-mentioned design, inventors herein propose following enforcement the present invention 2 class technical scheme:
Technical scheme 1: initiator and aromatic ring-shaped thioketones (C=S-Ph2 (X)) polymerization system select traditional radical initiator and aromatic ring-shaped thioketones (C=S-Ph2 (X)) under protection of inert gas; heating for some time, obtain the polymkeric substance containing active end group.、
The mechanism of initiator and aromatic ring-shaped thioketones (C=S-Ph2 (X)) polymerization system, as shown in (3), only causes a kind of monomer polymerization for C=S-Ph2 (S).From reaction mechanism, in the chainpropagation stage, establish the balance of thioketones-chain free radical fracture coupling, the existence of this balance just, makes the carbon radicals of most of propagating radical and carbon sulphur double bond and benzyl position be combined into dormancy chain state, only has a small amount of macromolecular chain free radical to be in active growth state, because propagating radical concentration is very low, be difficult to double-basis or disproportionation termination, thus react by controlled activity dynamics mechanism, obtain molecular weight and the controlled polymkeric substance that distributes.
Technical scheme 2: macromole evocating agent is initiated polymerization again
Homopolymer prepared by operation technique scheme 1 is macromole evocating agent, joins in the polymerization system containing other monomers, under protection of inert gas, heating for some time, can prepare block polymer.
In above-mentioned 2 kinds of technical schemes, main use can participate in the monomer of radical polymerization, as methacrylate-based monomer (as methyl methacrylate), acrylic ester monomer (as methyl acrylate), styrene monomer (as alpha-methyl styrene), vinyl acetate between to for plastic esters monomer (as vinyl acetate), acrylic monomer (as methacrylic acid), olefin monomer (as n-butene), anhydrides monomer (as maleic anhydride), one or more in amides monomer (as acrylamide).
In above-mentioned 2 kinds of technical schemes, polymerization process can be: body, solution, emulsion, reversed-phase emulsion, suspension or precipitation heterogeneous polymerization.
By above-mentioned 2 kinds of technical schemes polymerization obtain such as formula the polymkeric substance shown in (2), be the homopolymer containing active end group or segmented copolymer, be also object of protection of the present invention, nuclear-magnetism result is as shown in Figure 2.
Accompanying drawing explanation
The nuclear magnetic spectrogram of Fig. 1 C=S-Ph2 (S)
Fig. 2 contains the nuclear magnetic spectrogram of the homopolymer of active end group
Embodiment
Further describe the present invention by the following examples, but embodiment does not limit protection scope of the present invention.
Embodiment 1: at differential responses temperature, thia thioketones regulation and control MMA solution polymerization.
In 100ml single port bottle, add thia thioketones 0.0500g, AIBN0.0164g, MMA5.0000g, and toluene 15g.After degassed three times of sealing freeze thawing, react 24 hours under 70 degree and 80 degree respectively.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, and after vacuum-drying, the transformation efficiency being recorded monomer by weighting method was linearly increased with the reaction times; Observe that molecular weight increases with the increase of monomer conversion by GPC, dispersion coefficient is substantially below 1.8.The living-radical polymers obtained can be used as macromole evocating agent to be continued to cause other monomer block copolymerization.
Shown in 70 degree of experimental result tables 1.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 27.2 | 41400 | 1.78 |
| 3 | 44.5 | 45100 | 1.75 |
| 5 | 58.1 | 46900 | 1.73 |
| 10 | 67.4 | 47300 | 1.73 |
| 24 | 72.1 | 48200 | 1.76 |
Shown in 80 degree of experimental result tables 2.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 36.1 | 42300 | 1.79 |
| 3 | 58.5 | 43700 | 1.81 |
| 5 | 76.2 | 44900 | 1.84 |
| 10 | 84.1 | 47300 | 1.83 |
| 24 | 91.5 | 49200 | 1.84 |
Embodiment 2: under different MMA concentration, thia thioketones regulation and control MMA solution polymerization.
In 100ml single port bottle, add thia thioketones, AIBN, MMA and toluene.Add thia thioketones, AIBN, MMA and toluene, AIBN, thia thioketones quality is respectively 0.0328g and 0.1000g; MMA quality is respectively 2.50g, 5.00g, 10.00g.MMA and toluene amount to 20.00g.Degassed three times of sealing freeze thawing, all reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, and after vacuum-drying, the monomer conversion being recorded two groups of experiments by weighting method is all linearly increased with the reaction times; Observe that molecular weight all increases with the increase of monomer conversion by GPC.
MMA concentration is that 12.5% experimental result is as shown in table 3.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 8.2 | 16,300 | 1.71 |
| 3 | 27.4 | 19,500 | 1.72 |
| 5 | 41.8 | 20,700 | 1.75 |
| 10 | 52.5 | 22,300 | 1.68 |
| 24 | 64.7 | 24,200 | 1.66 |
MMA concentration is that 25% experimental result is as shown in table 4.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 33.5 | 41,400 | 1.78 |
| 3 | 52.9 | 45,100 | 1.76 |
| 5 | 66.4 | 45,500 | 1.73 |
| 10 | 72.1 | 47,400 | 1.76 |
| 24 | 93.9 | 48,000 | 1.82 |
MMA concentration is that 50% experimental result is as shown in table 5.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 21.8 | 77,100 | 1.74 |
| 3 | 37.1 | 85,800 | 1.71 |
| 5 | 48.6 | 90,700 | 1.73 |
| 10 | 65.3 | 95,200 | 1.71 |
| 24 | 72.4 | 96,700 | 1.83 |
Embodiment 3:70 degree thia thioketones regulation and control BA solution polymerization
In 100ml single port bottle, thia thioketones 0.0500g, AIBN0.0164g, BA5.00g, and toluene 15.00g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion increase with reaction times prolongation by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC, dispersion coefficient is about 1.8.The reactive polymer obtained can cause other monomer block copolymerization again as macromole evocating agent.
Experimental result is as shown in table 6.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 14.1 | 5,500 | 1.39 |
| 3 | 27.2 | 6,400 | 1.41 |
| 5 | 41.5 | 7,700 | 1.42 |
| 10 | 53.3 | 8,300 | 1.49 |
| 24 | 61.9 | 8,500 | 1.61 |
| 48 | 70.2 | 8,700 | 1.77 |
Embodiment 4:70 degree thia thioketones regulation and control GMA solution polymerization
In 100ml single port bottle, thia thioketones 0.0500g, AIBN0.0164g, GMA5.00g, and toluene 15.00g.。After degassed three times of sealing freeze thawing, react 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion extend slowly growth with the reaction times by weighting method.
Experimental result is as shown in table 7.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 11.9 | 22,000 | 1.22 |
| 2 | 16.3 | 27,100 | 1.26 |
| 3 | 21.2 | 31,400 | 1.24 |
| 4 | 25.9 | 32,100 | 1.26 |
| 5 | 27.1 | 37,900 | 1.32 |
Embodiment 5: oxa-thioketones regulation and control MMA solution polymerization
In 100ml single port bottle, oxa-thioketones 0.0212g, AIBN0.0082g, MMA5.00g, and toluene 15.00g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in table 8.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 13.6 | 42,800 | 1.76 |
| 3 | 33.2 | 45,300 | 1.71 |
| 5 | 57.9 | 46,600 | 1.74 |
| 10 | 68.3 | 50,100 | 1.74 |
| 24 | 73.9 | 51,200 | 1.77 |
| 36 | 77.2 | 51,300 | 1.76 |
| 48 | 88.5 | 51,400 | 1.77 |
Embodiment 6: oxa-thioketones regulation and control BA solution polymerization
In 100ml single port bottle, add oxa-thioketones 0.0212g, AIBN0.0082g, BA10.00g, and toluene 10.00g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in table 9.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 14.1 | 33,800 | 1.54 |
| 3 | 36.0 | 35,300 | 1.66 |
| 5 | 68.2 | 44,700 | 1.63 |
| 10 | 74.9 | 45,500 | 1.74 |
| 24 | 83.1 | 48,100 | 1.77 |
| 36 | 85.5 | 48,300 | 1.76 |
| 48 | 90.2 | 48,400 | 1.77 |
Embodiment 7: oxa-thioketones regulation and control GMA solution polymerization
In 100ml single port bottle, thioketones 0.0212g, AIBN0.0082g, GMA2.50g, and toluene 17.50g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in table 10.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 4.9 | 4,700 | 1.23 |
| 2 | 8.1 | 4,800 | 1.26 |
| 3 | 10.2 | 4,900 | 1.22 |
| 4 | 13.9 | 5,600 | 1.27 |
Embodiment 8: oxa-thioketones macromole evocating agent causes MMA polymerization
In 100ml single port bottle, add macromole evocating agent 1g, MMA2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in table 11.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 7,200 | 1.57 |
| 5 | 6.9 | 7,800 | 1.76 |
| 10 | 11.2 | 8,200 | 1.77 |
| 24 | 21.9 | 8,500 | 1.81 |
| 36 | 36.5 | 9,200 | 1.77 |
| 48 | 49.7 | 9,500 | 1.79 |
Embodiment 9: oxa-thioketones macromole evocating agent inducing B A is polymerized
In 100ml single port bottle, add macromole evocating agent 1g, BA2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in table 12.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 7,200 | 1.57 |
| 5 | 9.1 | 8,800 | 1.93 |
| 10 | 20.4 | 8,900 | 1.96 |
| 24 | 33.8 | 11,700 | 2.14 |
| 36 | 47.6 | 14,000 | 2.23 |
| 48 | 65.2 | 14,900 | 2.06 |
Embodiment 10: thia thioketones macromole evocating agent inducing B A is polymerized.
In 100ml single port bottle, add macromole evocating agent 1g, BA2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in table 13.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 5,800 | 1.27 |
| 5 | 13.2 | 7,100 | 1.44 |
| 10 | 21.1 | 8,300 | 1.61 |
| 24 | 37.5 | 8,500 | 1.57 |
| 36 | 54.0 | 10,200 | 1.72 |
| 48 | 79.4 | 17,100 | 1.68 |
Embodiment 11: thia thioketones macromole evocating agent causes MMA polymerization.
In 100ml single port bottle, add macromole evocating agent 1g, MMA2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in table 14.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 5,800 | 1.27 |
| 5 | 16.1 | 7,700 | 1.47 |
| 10 | 31.7 | 8,600 | 1.62 |
| 24 | 47.0 | 8.900 | 1.56 |
| 36 | 59.2 | 12,100 | 1.58 |
| 48 | 68.9 | 13,600 | 1.59 |
Embodiment 12: thia thioketones macromole evocating agent regulation and control TBMA polymerization.
In 100ml single port bottle, add macromole evocating agent 1g, TBMA2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in Table 15.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 5,800 | 1.27 |
| 5 | 11.1 | 6,100 | 1.32 |
| 10 | 17.2 | 6,700 | 1.36 |
| 24 | 29.4 | 6,900 | 1.44 |
| 36 | 40.7 | 7,600 | 1.41 |
| 48 | 48.5 | 8,300 | 1.47 |
Embodiment 13: sec.-propyl-thia thioketones regulation and control MMA polymerization
In 100ml single port bottle, sec.-propyl-thia thioketones 0.0544g, AIBN0.0164g, MMA5.0000g, and toluene 15g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 16.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 42.1 | 18,700 | 1.96 |
| 3 | 61.8 | 18,800 | 1.96 |
| 5 | 74.7 | 19,200 | 1.97 |
| 10 | 79.9 | 19,300 | 2.41 |
| 24 | 93.5 | 19,400 | 2.28 |
Embodiment 14: sec.-propyl-thia thioketones regulation and control polymerization
In 100ml single port bottle, thioketones 0.0544g, AIBN0.0164g, MMA5.0000g, and toluene 15g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 17.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 40.6 | 18,300 | 2.12 |
| 3 | 57.6 | 18,700 | 2.17 |
| 5 | 64.0 | 19,200 | 2.20 |
| 10 | 73.1 | 19,400 | 2.11 |
| 24 | 79.1 | 20,200 | 2.43 |
Embodiment 15: sec.-propyl-thia thioketones regulation and control GMA polymerization
In 100ml single port bottle, sec.-propyl-thia thioketones 0.0544g, AIBN0.0164g, MMA5.0000g, and toluene 15g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 18.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 17.1 | 66,300 | 1.44 |
| 3 | 32.8 | 72,900 | 1.55 |
| 5 | 43.5 | 87,300 | 1.52 |
| 10 | 51.8 | 91,400 | 1.55 |
Embodiment 16:4-hydroxyl-oxa-thioketones regulation and control MMA solution polymerization
In 100ml single port bottle, thioketones 0.0544g, AIBN0.0164g, MMA5.0000g, and toluene 15g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 19.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 10.5 | 8,000 | 1.75 |
| 3 | 22.6 | 10,200 | 1.79 |
| 5 | 35.9 | 12,600 | 1.78 |
| 10 | 50.2 | 15,500 | 1.76 |
| 24 | 62.9 | 16,900 | 1.77 |
Embodiment 17:4-hydroxyl-oxa-thioketones regulation and control BA solution polymerization
In 100ml single port bottle, thioketones 0.0544g, AIBN0.0164g, MMA5.0000g, and toluene 15g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 20.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 15.5 | 8,900 | 1.91 |
| 3 | 29.6 | 13,200 | 1.95 |
| 5 | 45.9 | 16,600 | 1.97 |
| 10 | 66.2 | 19,300 | 1.94 |
| 24 | 82.9 | 26,100 | 1.95 |
Embodiment 18:70 degree thia thioketones regulation and control St solution polymerization
In 100ml single port bottle, thioketones 0.0500g, AIBN0.0164g, St5.00g, and toluene 15.00g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion increase with reaction times prolongation by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC, dispersion coefficient is about 1.3.The reactive polymer obtained can cause other monomer block copolymerization again as macromole evocating agent.
Experimental result is shown in table 21.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 7.4 | 4,500 | 1.19 |
| 3 | 11.6 | 5,400 | 1.21 |
| 5 | 17.9 | 5,900 | 1.25 |
| 10 | 29.2 | 7,700 | 1.27 |
| 24 | 33.5 | 8,100 | 1.29 |
| 48 | 42.8 | 8,400 | 1.31 |
Embodiment 19:4-hydroxyl-oxa-thioketones regulation and control St solution polymerization
In 100ml single port bottle, thioketones 0.0544g, AIBN0.0164g, St2.0000g, and toluene 18g.Degassed three times of sealing freeze thawing, reacts 24 hours under 70 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 22.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 11.2 | 6,900 | 1.41 |
| 3 | 17.9 | 8,800 | 1.44 |
| 5 | 31.0 | 9,200 | 1.40 |
| 10 | 44.3 | 9,900 | 1.42 |
| 24 | 60.7 | 10,700 | 1.46 |
Embodiment 20: oxa-thioketones regulation and control St solution polymerization
In 100ml single port bottle, thioketones 0.0212g, AIBN0.0082g, St2.50g, and toluene 17.50g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 23.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 5.7 | 3,700 | 1.23 |
| 2 | 10.4 | 4,200 | 1.26 |
| 3 | 19.6 | 4,900 | 1.22 |
| 4 | 28.7 | 5,300 | 1.27 |
Embodiment 21: thia thioketones regulation and control MMA mass polymerization
In 100ml single port bottle, thioketones 0.0212g, AIBN0.0082g, MMA20g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 24.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 5.2 | 156,900 | 1.66 |
| 3 | 11.9 | 163,800 | 1.71 |
| 5 | 19.0 | 171,200 | 1.74 |
| 10 | 22.5 | 179,900 | 1.72 |
| 24 | 34.1 | 186,700 | 1.75 |
Embodiment 22: thia thioketones regulation and control BA mass polymerization
In 100ml single port bottle, thioketones 0.0212g, AIBN0.0082g, BA20g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is as shown in Table 25.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 1 | 5.2 | 176,700 | 1.88 |
| 3 | 11.9 | 183,400 | 1.89 |
| 5 | 19.0 | 187,100 | 1.94 |
| 10 | 22.5 | 192,300 | 1.96 |
| 24 | 34.1 | 196,000 | 1.95 |
Embodiment 23: thia thioketones macromole evocating agent (PBA) regulates and controls MMA polymerization
In 100ml single port bottle, add macromole evocating agent PBA1g, MMA2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 26.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 7,400 | 1.47 |
| 5 | 17.5 | 9,100 | 1.56 |
| 10 | 29.7 | 10,500 | 1.61 |
| 24 | 41.0 | 13,200 | 1.64 |
| 36 | 53.2 | 15,700 | 1.65 |
| 48 | 66.9 | 16,900 | 1.62 |
Embodiment 24: thia thioketones macromole evocating agent (PBA) regulates and controls GMA polymerization
In 100ml single port bottle, add macromole evocating agent PBA1g, GMA2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 27.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 7,400 | 1.47 |
| 5 | 2.2 | 7,700 | 1.46 |
| 10 | 5.6 | 8,100 | 1.51 |
| 24 | 9.9 | 8,400 | 1.53 |
| 36 | 13.8 | 8,500 | 1.55 |
| 48 | 16.3 | 8,800 | 1.59 |
Embodiment 25: thia thioketones macromole evocating agent (PBA) regulates and controls St polymerization
In 100ml single port bottle, add macromole evocating agent PBA1g, St2g, toluene 7g.Degassed three times of sealing freeze thawing, reacts 24 hours under 80 degree.Timing is taken out sample and it is placed in rapidly liquid nitrogen quenching, after vacuum-drying, records monomer conversion linearly increase with the reaction times by weighting method; Observe that molecular weight increases with the increase of monomer conversion by GPC.
Experimental result is shown in table 28.
| Time (hour) | Transformation efficiency (%) | Molecular weight | Polydispersity coefficient |
| 0 | 0 | 7,400 | 1.47 |
| 5 | 6.7 | 8,200 | 1.49 |
| 10 | 12.5 | 8,900 | 1.51 |
| 24 | 21.9 | 9,300 | 1.52 |
| 36 | 33.1 | 9,500 | 1.55 |
| 48 | 49.7 | 9,800 | 1.53 |
Claims (7)
1. by the assorted thioketones of aromatic ring-shaped sulphur (oxygen) and derivative thereof and radical initiator and an active free radical polymerization method, it is characterized in that comprising the following steps:
(1), in the mixture formed at one or more monomers, add such as formula one or more in the initiation control agent shown in (1), form dual initiator polymerization system trigger monomer with all kinds of thermal free radical initiator and react; Causing control agent is that 1:50-50:1 mixes with thermal free radical initiator mol ratio;
In formula (1), R substituent is H, halogen, alkyl, carboxyl, aldehyde radical, cyano group or methoxyl group; R accounts for phenyl ring 1, any one or multiple position of 2,3,4, and X substituting group is C, N, O, S, P;
(2) according to initiation control agent and monomer mole ratio be 1:10-1:100000, thermal free radical initiator and initiator control agent and monomer are together placed in reaction flask, after the degassed or logical nitrogen deoxygenation of sealing freeze thawing, 4-72 hour is reacted under 40-150 degree, obtain the polymkeric substance that molecular weight and molecualr weight distribution is all controlled, shown in (2);
In formula (2), polymerization degree m, n=1-1000, wherein X is the one in C, N, O, P, S; R
1, R
2, R
3, R
4for the different substituents of various monomer.
2. the method for claim 1, it is characterized in that: using obtained above such as formula the polymkeric substance shown in (2) as macromole evocating agent, add one or more monomers again, adopt different polymerization processs respectively, all can obtain the chain extension obtaining structure-controllable or block polymer.
3. the method for claim 1, is characterized in that:
Polymerization process is body, solution, emulsion, reversed-phase emulsion, suspension or precipitation heterogeneous polymerization.
4. the method for claim 1, is characterized in that:
Described monomer is methacrylate-based monomer, acrylic ester monomer, styrene monomer, vinyl acetate between to for plastic esters monomer, acrylic monomer, olefin monomer, anhydrides monomer, one or more in amides monomer.
5. the method for claim 1, is characterized in that:
Described monomer is methyl methacrylate, methyl acrylate, alpha-methyl styrene, vinyl acetate, methacrylic acid, n-butene, maleic anhydride, one or more in acrylamide.
6. the method for claim 1, is characterized in that:
Cause control agent and adopt thia thioketones.
7. the polymkeric substance obtained prepared by the method for claim 1, shown in (2);
In formula (2), polymerization degree m, n=1-1000, wherein X is the one in C, N, O, P, S; R
1, R
2, R
3, R
4for the different substituents of various monomer.
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| CN107522686A (en) * | 2017-08-25 | 2017-12-29 | 北京化工大学 | Sulfide compound and preparation method thereof |
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