CN1159344C - Method for preparing gradient copolymer - Google Patents
Method for preparing gradient copolymer Download PDFInfo
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- CN1159344C CN1159344C CNB00136085XA CN00136085A CN1159344C CN 1159344 C CN1159344 C CN 1159344C CN B00136085X A CNB00136085X A CN B00136085XA CN 00136085 A CN00136085 A CN 00136085A CN 1159344 C CN1159344 C CN 1159344C
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Abstract
The present invention provides a method for preparing a gradient copolymer. Organic halide is used as an initiating agent. The halide of low-valent ion of a transitional metal or a transitional metal is used as a catalyst, and di(2-dimethylaminoethyl)ether(BDE) or the derivative of the di(2-dimethylaminoethyl)ether(BDE) is used as a coordination agent. By respectively adopting a reaction material feeding method and a one-time material charging method, a gradient copolymer is synthesized. The method of the present invention has the advantages of mild reaction condition, low price of raw materials, wide material source, easy operation and wide application range of a monomer. In the method of the present invention, the gradient copolymer in which the molecular structure is clear and can be controlled, monomer ratio, composition and copolymer number-average molecular weight can be adjusted and molecular weight distribution is narrow.
Description
Technical field
The present invention relates to a kind of method for preparing multipolymer, more particularly, the present invention relates to a kind of method for preparing gradient copolymer.
Background technology
So-called gradient copolymer (gradient polymer), also claim " gradual change multipolymer " or " tapered block copolymer ", refer to microcosmic and form with the increase of multipolymer chain length to occupy an leading position and change to the prevailing multipolymer of another kind of monomer from a kind of monomer.
Since gradient copolymer in 1966 was by reported first, scientist had carried out a series of researchs to it, for example can be referring to people's such as G.Holden U.S. Patent No. 3 265 765 (1966); People such as Tamio Tsukahara,
Polymkeric substance periodical (Polyn.J.), 1980,12:455; People such as K.Sardelis,
Polymkeric substance (Polymer), 1987,28:244; People such as John M.Zielinski,
Macromole (Macromolecular), 1992,25:5957; And people such as A.V.Olenin,
Polymkeric substance communication (Polym.Bull.), 1992,28:449.
In view of some unique textures and the performance of gradient copolymer, it can be used for aspects such as the modification of polymkeric substance and binding agent, can replace random, block, alternating copolymer to be applied to the improvement of the interface avidity of incompatible multipolymer, even to obtain better effect.Certainly, gradient copolymer can also show the performance of its brilliance in polymer interface enhancing field.As seen, the practical application of gradient copolymer and industrial prospect are very wide.
But the limitation of the method for traditional preparation process gradient copolymer has limited further developing of it again, mainly shows the following aspects:
1. anionoid polymerization condition harshness is formed though the gradient copolymer that obtains has gradient in the middle of segment, can not obviously be better than segmented copolymer on performance; In addition, the graded of component is spontaneous and wayward.
2. the gradient copolymer polydispersity coefficient (Mw/Mn) that obtains of specific initiator radical polymerization is big, generally greater than 2; Specific initiator is synthetic quite difficult in addition.
Then overcome above shortcoming with ATRP technology composition gradient multipolymer.Nineteen ninety-five, Wang Jinshan and K Matyjaszewski.
At JACS (Journal of American Chemistry Society), 1995,117 (20): proposed a kind of novel active polymerization process among the 5614-5615, be referred to as atom transfer radical polymerization, i.e. ATRP.ATRP is to be initiator with the halogenated alkyl hydrocarbon, and transistion metal compound is a catalyzer, and bipyridine is a coordination agent, 60 ℃-130 ℃ polyreactions that cause vinyl monomers down.The molecular weight distribution of the polymeric articles that obtains is 1.03 to 1.5.Because ATRP compared with former " activity " free radical polymerisation process and has molecular weight and can be controlled by initiator concentration, and reach as high as 105 characteristics, therefore this technology is once report, the scientists that various countries are engaged in living polymerization research gives high evaluation one after another, thinking an invention of great significance of polymer synthetic chemistry circle in decades, is the very important breakthrough in " activity " radical polymerization field.People have utilized the ATRP technology to prepare block, grafting, star, random and gradient polymer.Wherein gradient polymer research is few, and DorotaGreszta exists
Polymkeric substance is preprinted collection (Polym.Prep), 1996,37 (1): synthesized St-BA, St-MA gradient copolymer with the reaction feed method in 569, and studied the influence of feed rate to segmented structure, molecular weight, polydispersity coefficient, second-order transition temperature etc.He finds, improves with monomer addition speed, and molecular weight of copolymer reduces, and second-order transition temperature raises, and segmented structure also has significant change.
Dorota Greszta thinks that when reactivity ratio of monomer was more or less the same, the preparation gradient copolymer need satisfy two conditions:
1. there is not chain termination reaction.The continuous growth of copolymer chain is the prerequisite that obtains the unified multipolymer of structure.
2. reaction is reinforced.Only in entire reaction course, add continuously second kind of monomer, just can obtain gradient-structure and reach the purpose of control.
And these two conditions have only ATRP just can realize up to now.
According to the reactivity ratio of monomer difference what, can prepare gradient copolymer with two kinds of diverse ways, be respectively a feeding method and react the feed method:
1. feeding method: when reactivity ratio of monomer differs greatly, in solvent, catalyzer, initiator, two kinds of disposable adding reactors of monomer, be heated to certain temperature, utilize reactivity ratio difference and monomer concentration to change, make the spontaneous generation gradient copolymer of system.
2. react the feed method: when reactivity ratio of monomer is more or less the same, in solvent, catalyzer, initiator, the disposable adding reactor of a kind of monomer, after being heated to certain temperature reaction beginning, add another kind of monomer by pump with certain flow again, control generates gradient copolymer.
1997, people such as Sephen V.Arehart existed
Polymkeric substance is preprinted collection (Polym.Prep), 1997,38 (1): also synthesized gradient copolymer in 705, but the monomer of their usefulness is vinylbenzene and butyl acrylate, and thinks by changing the purpose that monomer adding speed can reach the Quality Initiative segment structure with the ATRP technology.
Coordination agent has the effect that increases catalyst dissolution performance and stable transition metal as ATRP reaction system important component part.The bipyridine that human bipyridine such as Dorota Greszta and Stephen V.Arehart or alkyl replace is as coordination agent composition gradient multipolymer, but above-mentioned coordination agent price is very expensive.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of reaction conditions gentleness is provided, raw material is cheap and easy to get, and is easy and simple to handle, the method for preparing gradient copolymer that monomer is applied widely.
The inventive method is the improvement to known ATRP technology, promptly adopt the ATRP technology, with Organohalogen compounds is initiator, with transition metal or transition metal low price ionic halogenide is catalyzer, with two (2-dimethyl amido ethyl) ether (BDE) or derivatives thereof is coordination agent, respectively with two kinds of method composition gradient multipolymers:
A) reaction feed method: when reactivity ratio of monomer is more or less the same, will be as in the disposable adding reactor of the first monomeric alefinically unsaturated compounds, add continuously as second monomeric other rare ethylenically unsaturated compounds with certain flow in entire reaction course, control generates gradient copolymer again;
B) feeding method: when reactivity ratio of monomer differs greatly, will utilize reactivity ratio difference and monomer concentration to change, and make the spontaneous generation gradient copolymer of system as in the disposable adding reactor of the first and second monomeric alefinically unsaturated compounds.
Below illustrate in greater detail the present invention.
Main preparation methods of the present invention is as follows: first method: a certain amount of solid catalyst and the coordination agent that add in the exsiccant reactor, pump drainage, inflated with nitrogen circulation 3 times, add first monomer, add initiator again, stir, the constant temperature oil bath reacting by heating adds second monomer by constant flow pump simultaneously; Second method: add a certain amount of solid catalyst and coordination agent in the exsiccant reactor, pump drainage, inflated with nitrogen circulation 3 times add first and second monomers, add initiator again, stir constant temperature oil bath heating initiated polymerization.
The monomer that can be used for the inventive method is an alefinically unsaturated compounds.Described alefinically unsaturated compounds is any alefinically unsaturated compounds that can carry out the ATRP polyreaction, and its specific examples comprises: vinylbenzene and derivative thereof, preferable methyl vinylbenzene, ethyl styrene, alpha-methyl styrene etc.; (methyl) vinylformic acid (alkyl ester) class and vinyl cyanide, preferred vinylformic acid, methacrylic acid, acrylate and methyl acrylic ester, for example methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate etc., or its arbitrary combination.In the methods of the invention, first monomer is preferably vinylbenzene and derivatives class thereof, is preferably vinyl toluene, ethyl styrene, alpha-methyl styrene etc.; (methyl) vinylformic acid (alkyl ester) class and vinyl cyanide, be preferably vinylformic acid, methacrylic acid, acrylate and methyl acrylic ester, for example methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, or its arbitrary combination.Described second monomer also is preferably selected from above-mentioned monomer but is different with first monomer.
The catalyzer that can be used for the inventive method can be alefinically unsaturated compounds any catalyzer commonly used when carrying out the ATRP polyreaction.Catalyzer is preferably transition metal or transition metal low price ionic halogenide, and the specific examples of catalyzer comprises transition metal Cu, Fe or their low price halogenide, is preferably CuCl, CuBr, FeCl
2, FeBr
2Deng, or its arbitrary combination.
The coordination agent that can be used for the inventive method is organic nitrogen-containing and the oxygen compound with one of following general structure:
R
1R
2NR
3OR
4NR
5R
6
Wherein: R
1, R
2, R
5And R
6Be aliphatic hydrocarbyl, the preferred alkyl that contains 1-20 carbon atom independently of each other, R
3And R
4Be the aliphatic alkylene that contains 2-6 carbon atom, preferred alkylidene group independently of each other.Preferred coordination agent has two (2-dimethyl amido ethyl) ether (BDE) and derivatives thereof.The specific examples of derivative has two (2-diethyl amido ethyl) ethers, two (2-dibutyl amido ethyl) ether, two (2-dimethyl amido propyl group) ether etc.
The initiator that can be used for the inventive method can be alefinically unsaturated compounds any initiator commonly used when carrying out the ATRP polyreaction, preferred organic halide-containing.Organic halide-containing initiator is preferably the organic halide-containing with one of following general structure especially:
Wherein, R is hydrogen atom, halogen atom, organic fatty family hydro carbons or aromatic substituents independently of each other, and molecular weight is less than 10,000; X is Cl or Br.The specific examples of organic halide-containing initiator comprises 2-methyl-2 bromopropionic acid ethyl ester, 2-bromo-butyric acid ethyl ester, the 2-ethyl bromoacetate, the 2 bromopropionic acid ethyl ester, 2-methyl-2-chloropropionate, the 2-neoprene acid ethyl ester, the 2-ethyl chloroacetate, ethyl trichloroacetate, 2-methyl-2 bromopropionic acid propyl ester, tetracol phenixin, benzyl chloride, bromotoluene, α-chlorine (generation) ditane, α-bromine (generation) ditane, Triphenyl methane chloride 99, the triphen monobromethane, p-methyl benzene sulfonic chloride, chlorallylene, allyl bromide 98 etc.
There is no particular restriction to the synthetic technological condition of gradient copolymer, but preferred synthetic technological condition is such:
The ratio of first monomer and initiator is 10～3000 (mol ratios), preferred 50～2000 (mol ratios).When adopting reaction feed method, the second monomeric feed rate is for per hour having added 0.001～10 times (mol ratio) of first amount of monomer, preferred 0.005～1 times (mol ratio).The ratio of first monomer and second monomer is 0.1～10 (mol ratio), preferred 0.5～5 (mol ratio).
The halogen in the initiator and the ratio of catalyzer are 0.1～4 (mol ratio), preferred 0.5～3 (mol ratio); The ratio of catalyzer and coordination agent is 1～5 (mol ratio), preferred 1.5～4 (mol ratios).
Not strict when implementing method of the present invention to the requirement of polymerization temperature, be generally 20 ℃～160 ℃, be preferably 60～140 ℃.Requirement to monomeric polymerization reaction time is not strict yet, can finish to about 96 hours time range at several minutes, is generally 1 hour～72 hours.
The inventive method can adopt body and solution polymerization process.
Can use conventional inertia attenuant in polymerization process, its representative instance has toluene, benzene, pimelinketone, dimethyl phthalate, dimethylbenzene etc.
As needs, can adopt conventional method to reclaim unreacted monomer and reaction product is purified, remove wherein catalyzer, coordination agent etc., the product after being purified, described gradient copolymer gel permeation chromatograph is analyzed number-average molecular weight and is generally 400～200000.
Polymerization process carries out under the protection of rare gas element (as nitrogen, argon gas and chlorine) usually.
It is clear controlled that the inventive method can make molecular structure, and monomer ratio and composition, multipolymer number-average molecular weight can be regulated arbitrarily and the gradient copolymer of narrow molecular weight distribution.And the inventive method adopts two (2-dimethyl amido ethyl), and ether (BDE) is as coordination agent composition gradient multipolymer, and BDE is cheap and easy to get, and its price is about one of percentage of bipyridine (Bpy), and toxicity is low.Except BDE was cheap and easy to get, the present invention also found with BED faster than using the Bpy polymerization velocity, and molecular weight of copolymer is higher.The inventive method also has the reaction conditions gentleness, the monomer advantage of wide range of application.Therefore, the inventive method greatly reduces the production cost of ATRP method, is very beneficial for the industrialization of ATRP method composition gradient multipolymer.
Below will the present invention is further illustrated by embodiment, but embodiment does not limit protection scope of the present invention.
In following examples, the monomer total conversion rate is determined with weighting method: total conversion rate=(polymkeric substance weight/sampling is heavy) * 100%; Multipolymer yield (y)=(multipolymer weight/monomer gross weight) * 100%; Number-average molecular weight Mn (GPC), molecular weight polydispersity coefficient MWD measure with Waters 50GPC/ALC gel permeation chromatograph, moving phase is tetrahydrofuran (THF), flow velocity 1.0ml/min, 25 ℃ of temperature, the monodisperse polystyrene of the known molecular amount that standard specimen provides for Waters company; The composition of multipolymer is analyzed CDCl with 500M 1H-NMR nuclear magnetic resonance analyser
3Be solvent.
Embodiment
Embodiment 1
In the exsiccant reactor, add solid catalyst CuBr (0.49mmol) and Cu (0.49mmol), pump drainage, inflated with nitrogen circulation 3 times, add two (2-dimethyl amido ethyl) ethers (0.96mmol), syringe through the degassing adds monomer styrene (96.6mmol), add initiator 2-isobutyl ethyl bromide (Eib-Br) subsequently (0.49mmol), open magnetic agitation, constant temperature oil bath is heated to 90 ℃, adds second monomers methyl methacrylate (MMA) by constant flow pump with the 0.73mmol/min flow simultaneously.After the reaction, reaction system is cooled to-10 ℃ and stops polyreaction.Every interval one end time sampling is analyzed in the polymerization process.
Fig. 1 is the graph of a relation of polymer output and polymerization time.As seen from the figure, with the prolongation of polymerization reaction time, polymer output increases, and reacts the later stage because MMA content increases, and hastening phenomenon has appearred in polyreaction.
Fig. 2 is the graph of a relation of number-average molecular weight and molecular weight polydispersity coefficient and polymer output.As seen from the figure, number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrate that this polyreaction has " activity " characteristic.
Table 1 is MMA structural unit content and multipolymer chain length mark in the multipolymer (polyreaction is to the number-average molecular weight of a certain moment sample number-average molecular weight divided by a final product) relation.As seen, along with MMA monomer content in the growth of the prolongation in reaction times and copolymer chain and the system increases, MMA structural unit content increases in the multipolymer.Illustrate that the synthetic multipolymer has gradient-structure.
MMA structural unit content and multipolymer chain length fractional relationship in table 1 multipolymer
| Sample number into spectrum | 1 | 2 | 3 |
| Polymerization time (minute) | 60 | 150 | 330 |
| The chain length mark | 0.153 | 0.455 | 1.000 |
| ％MMA | 0.191 | 0.320 | 0.500 |
Comparative Examples 1
In the reactor identical with embodiment 1, add CuBr (0.49mmol), Cu (0.49mmol), 2 successively, 2 '-bipyridine (bpy) (0.96mmol), vinylbenzene (96.6mmol) and 2-isobutyl ethyl bromide (Eib-Br) (0.49mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add MMA with the 0.81mmol/min flow, all the other processes are with embodiment 1.Experimental result sees Table 2.
Comparative Examples 2
In the reactor identical with embodiment 1, add successively CuBr (0.49mmol), Cu (0.49mmol), phenanthroline (phen) (0.96mmol), vinylbenzene (96.6mmol) and 2-isobutyl ethyl bromide (Eib-Br) (0.49mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add MMA with the 0.60mmol/min flow, all the other processes are with embodiment 1.Experimental result sees Table 2.
Table 2 enumerated two (the 2-dimethyl amido ethyl) ethers (BDE), 2,2 of different coordination agents '-data that bipyridine (bpy) and phenanthroline (phen) synthesize P (St-t-MMA).Add the MMA monomer methods continuously owing to adopt, and monomer polymerization speed adds speed less than monomer, last stage reaction has been accumulated more MMA monomer, makes monomer conversion not high.Relatively as seen, the St/BDE/CuBr/Cu/Eib-Br polymerization-filling is fastest, and the products therefrom molecular weight is the highest, and molecular weight had reached 4.22 * 10 in 330 minutes
4St/phen/CuBr/Cu/Eib-Br system molecular weight of copolymer polydispersity coefficient minimum be 1.31, but polymerization velocity is slower.And the molecular weight of copolymer polydisperse system number average that other two kinds of polymerization systems obtain greater than 1.44 less than 1.5.
The data of the synthetic P (St-t-MMA) of the different coordination agents of table 2
| Coordination agent | BDE | Bpy | Phen |
| The MMA feed rate, mmole/minute | 0.73 | 0.81 | 0.60 |
| Temperature, ℃ | 90 | 90 | 110 |
| Reaction times, minute | 330 | 330 | 405 |
| Transformation efficiency, % | 31.5 | 31.0 | 36.2 |
| Mn (theoretical value) | 21696 | 22980 | 20464 |
| Mn(GPC) | 42200 | 29800 | 29300 |
| Efficiency of initiation | 0.51 | 0.77 | 0.70 |
| MWD | 1.49 | 1.44 | 1.31 |
| When reacting 30 minutes, accumulation %MMA | 0.19/60 minute | 0.38 | 0.20 |
| When reaction finishes, accumulation %MMA | 0.50 | 0.60 | 0.42 |
Embodiment 2
In the reactor identical with embodiment 1, by the BDE/CuBr/Cu/Eib-Br proportioning is 4/1/1/1 to add CuBr (0.49mmol), Cu (0.49mmol), BDE (1.92mmol), vinylbenzene (96.6mmol) and 2-isobutyl ethyl bromide (Eib-Br) successively (0.49mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add MMA with the 1.06mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .5 hour, MMA structural unit content is 37.1% in the multipolymer, and when polymerization stopped in 5.5 hours, MMA structural unit content was 64.2% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=7.64 of gradient copolymer * 10
4, MWD=1.47.
Embodiment 3
In the reactor identical with embodiment 1, by the BDE/CuBr/Cu/Eib-Br proportioning is 4/2/2/1 to add CuBr (0.98mmol), Cu (0.98mmol), BDE (1.92mmol), vinylbenzene (96.6mmol) and 2-isobutyl ethyl bromide (Eib-Br) successively (0.49mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add MMA with the 1.58mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .5 hour, MMA structural unit content is 35.1% in the multipolymer, and when polymerization stopped in 5.5 hours, MMA structural unit content was 64.2% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=8.22 of gradient copolymer * 10
4, MWD=1.52.
Embodiment 4
In the reactor identical with embodiment 1, by the BDE/CuCl/Enp-Br proportioning is 3/1/1 to add CuCl (0.017mmol), BDE (0.051mmol), vinylbenzene (33.2mmol) and 2-isobutyl ethyl bromide (Enp-Br) successively (0.017mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add MMA with the 0.008mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows that polymerization is in the time of 1 hour, and MMA structural unit content is 8.3% in the multipolymer, and when polymerization stopped in 6 hours, MMA structural unit content was 28.7% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=0.68 of gradient copolymer * 10
4, MWD=1.48.
Embodiment 5
In the reactor identical with embodiment 1, by the BDE/CuBr/Eib-Br proportioning is 2/1/1 to add CuBr (0.49mmol), BDE (0.96mmol), vinylbenzene (96.6mmol) and 2-isobutyl ethyl bromide (Eib-Br) successively (0.49mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add MMA with the 1.06mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .5 hour, MMA structural unit content is 29.2% in the multipolymer, and when polymerization stopped in 5.5 hours, MMA structural unit content was 57.1% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=1.95 of gradient copolymer * 10
4, MWD=1.22.
Embodiment 6
In the reactor identical with embodiment 1, by the BDE/Cu/Eib-Br proportioning is 2/1/1 to add Cu (0.49mmol), BDE (0.96mmol), vinylbenzene (96.6mmol) and 2-isobutyl ethyl bromide (Eib-Br) successively (0.49mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add MMA with the 1.06mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .5 hour, MMA structural unit content is 26.3% in the multipolymer, and when polymerization stopped in 5.5 hours, MMA structural unit content was 49.2% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=7.90 of gradient copolymer * 10
4, MWD=1.38.
Embodiment 7
In the reactor identical with embodiment 1, by BDE/Cu/ bromotoluene proportioning is that 0.5/0.25/1 adds Cu (0.49mmol), BDE (0.96mmol), vinyl toluene (386.4mmol) and bromotoluene (1.96mmol) successively, place 160 ℃ of oil bath heating to carry out polyreaction, add MMA with the 4.2mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .1 hour, MMA structural unit content is 4.2% in the multipolymer, and when polymerization stopped in 1 hour, MMA structural unit content was 28.6% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=0.45 of gradient copolymer * 10
4, MWD=1.20.
Embodiment 8
In the reactor identical, press BDE/Cu/FeCl with embodiment 1
2/ p-methyl benzene sulfonic chloride proportioning is 10/1/3/1 to add Cu (0.49mmol), FeCl successively
2(1.47mmol), BDE (4.8mmol), ethyl styrene (96.6mmol) and p-methyl benzene sulfonic chloride (0.49mmol), place 90 ℃ of oil baths heating to carry out polyreaction, add vinyl cyanide with the 0.02mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows that polymerization is in the time of 1 hour, and acrylonitrile unit unit content is 5.2% in the multipolymer, and when polymerization stopped in 6 hours, acrylonitrile unit unit content was 24.3% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=2.54 of gradient copolymer * 10
4, MWD=1.52.
Embodiment 9
In the reactor identical, press BDE/Cu/FeBr with embodiment 1
2/ tetracol phenixin proportioning is 6/1/3/1 to add Cu (0.49mmol), FeBr successively
2(1.47mmol), BED (2.88mmol), alpha-methyl styrene (96.6mmol) and tetracol phenixin (0.49mmol), place 90 ℃ of oil bath heating to carry out polyreaction, add Propylene glycol monoacrylate and butyl acrylate (1/10 mol ratio) with the 1.06mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value, illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows, polymerization is in the time of 1 hour, and hydroxyethyl methylacrylate and butyl acrylate structural unit content are 12.8% in the multipolymer, when polymerization stopped in 6 hours, MMA structural unit content is 45.3% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=3.65 of gradient copolymer * 10
4, MWD=1.48.
Embodiment 10
In the reactor identical with embodiment 1, by BDE/Fe/CuBr/ ethyl trichloroacetate proportioning is 6/1/3/1 to add Fe (0.49mmol), CuBr (1.47mmol), BDE (2.88mmol), butyl acrylate (96.6mmol) and ethyl trichloroacetate (0.49mmol) successively, place 140 ℃ of oil bath heating to carry out polyreaction, add vinylformic acid and methyl methacrylate (0.5/10 mol ratio) with the 0.82mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value (about 1.5), illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows, in the time of polymerase 10 .5 hour, vinylformic acid and methyl methacrylate structural unit content are 8.5% in the multipolymer, when polymerization stopped in 6 hours, vinylformic acid and methyl methacrylate structural unit content are 32.6% in the multipolymer, illustrate that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=8.36 of gradient copolymer * 10
4, MWD=1.54.
Embodiment 11
In the reactor identical with embodiment 1, by BDE/CuBr/Cu/ allyl bromide 98 proportioning is 4/2/2/1 to add CuBr (0.98mmol), Cu (0.98mmol), BDE (1.92mmol), p-methylstyrene (96.6mmol) and allyl bromide 98 (0.49mmol) successively, place 40 ℃ of oil bath heating to carry out polyreaction, add methacrylic acid and methyl acrylate (0.5/10 mol ratio) with the 0.01mmol/min flow, all the other processes are with embodiment 1.Experimental result shows that number-average molecular weight and polymer output are linear, and the molecular weight polydispersity coefficient maintains smaller value, illustrates that this polyreaction is controlled.The nuclear-magnetism test analysis shows, polymerization is in the time of 5 hours, and methacrylic acid and methyl acrylate structural unit content are 15.1% in the multipolymer, when polymerization stopped in 64 hours, methacrylic acid and methyl acrylate structural unit content are 48.2% in the multipolymer, illustrate that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=5.26 of gradient copolymer * 10
4, MWD=1.49.
Embodiment 12
In the reactor identical with embodiment 1, by the BDE/CuBr/Cu/Eib-Br proportioning is 4/2/2/1 to add CuBr (0.98mmol), Cu (0.98mmol), BDE (1.92mmol), vinylbenzene (386.4mmol) and hydroxyethyl methylacrylate (386.4mmol) and 2-isobutyl ethyl bromide (Eib-Br) successively (0.49mmol), place 60 ℃ of oil bath heating to carry out polyreaction, all the other processes are with embodiment 1.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .5 hour, styrol structural unit content is 15.1% in the multipolymer, and styrol structural unit content was 36.2% in the multipolymer, illustrated that polymer product is a gradient copolymer when stopping in polyase 13 .5 hour.GPC surveys molecular weight, the Mn=8.62 of gradient copolymer * 10
3, MWD=1.55.
Embodiment 13
In the reactor identical with embodiment 1, by the BDE/CuBr/Cu/Eib-Br proportioning is 4/2/2/1 to add CuBr (0.98mmol), Cu (0.98mmol), BDE (1.92mmol), butyl acrylate (386.4mmol) and hydroxyethyl methylacrylate (193.2mmol) and 2-isobutyl ethyl bromide (Eib-Br) successively (0.49mmol), place 80 ℃ of oil bath heating to carry out polyreaction, all the other processes are with embodiment 1.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .5 hour, butyl acrylate architecture unit content is 18.1% in the multipolymer, and when polymerization stopped in 4.5 hours, butyl acrylate structural unit content was 46.2% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=7.64 of gradient copolymer * 10
4, MWD=1.49.
Embodiment 14
In the reactor identical with embodiment 1, by the BDE/CuBr/Cu/Eib-Br proportioning is 4/2/2/1 to add CuBr (0.98mmol), Cu (0.98mmol), BDE (1.92mmol), vinylbenzene (772.8mmol) and Rocryl 410 (193.2mmol) and 2-isobutyl ethyl bromide (Eib-Br) successively (0.49mmol), place 60 ℃ of oil bath heating to carry out polyreaction, all the other processes are with embodiment 1.The nuclear-magnetism test analysis shows that in the time of polymerase 10 .6 hour, styrol structural unit content is 25.1% in the multipolymer, and when polymerization stopped in 4.5 hours, styrol structural unit content was 56.2% in the multipolymer, illustrates that polymer product is a gradient copolymer.GPC surveys molecular weight, the Mn=4.68 of gradient copolymer * 10
3, MWD=1.42.
Claims (17)
1. the method for a composition gradient multipolymer is characterized in that:
With Organohalogen compounds is initiator, is catalyzer with transition metal or transition metal low price ionic halogenide, is coordination agent with two (2-dimethyl amido ethyl) ether or derivatives thereof, respectively with two kinds of method composition gradient multipolymers:
A) reaction feed method: when reactivity ratio of monomer is more or less the same, will be as in the disposable adding reactor of the first monomeric alefinically unsaturated compounds, add continuously as the second monomeric other alefinically unsaturated compounds with certain flow in entire reaction course, control generates gradient copolymer again;
B) feeding method: when reactivity ratio of monomer differs greatly, will utilize reactivity ratio difference and monomer concentration to change, and make the spontaneous generation gradient copolymer of system as in the disposable adding reactor of the first and second monomeric alefinically unsaturated compounds;
Wherein in above two kinds of synthetic methods, described first monomer and second kind of monomer are selected from vinylbenzene and derivative thereof, vinylformic acid, methacrylic acid, acrylate, methacrylic ester and vinyl cyanide, and condition is two kinds of monomer differences; And
Wherein the mol ratio of monomer total amount and initiator is 10～3000; When adopting reaction feed method, the second monomeric feed rate is counted 0.001～10 times that has per hour added first amount of monomer with molar weight; First monomer and the second monomeric mol ratio are 0.1～10.
2. the method for claim 1 is characterized in that, described first monomer and second kind of monomer are selected from vinylbenzene and derivative thereof, and condition is two kinds of monomer differences.
3. the method for claim 1 is characterized in that, described initiator is the Organohalogen compounds with one of following general structure:
Wherein, R is a hydrogen atom, halogen atom, and in organic fatty family alkyl or the aromatic substituents one, molecular weight is less than 10,000; X is Cl or Br.
4. the method for claim 1 is characterized in that, the mol ratio of monomer total amount and initiator is 50～2000.
5. the method for claim 1 is characterized in that, when adopting the reaction feed, the second monomeric feed rate is counted 0.005～1 times that has per hour added first amount of monomer with molar weight.
6. the method for claim 1 is characterized in that, first monomer and the second monomeric mol ratio are 0.5～5.
7. the method for claim 1 is characterized in that, the halogen in the initiator and the mol ratio of catalyzer are 0.1～4; The mol ratio of catalyzer and coordination agent is 1～5.
8. method as claimed in claim 7 is characterized in that, the halogen in the initiator and the mol ratio of catalyzer are 0.5～3.
9. method as claimed in claim 7 is characterized in that, the mol ratio of catalyzer and coordination agent is 1.5～4.
10. the method for claim 1 is characterized in that, the polymerization temperature of employing is 20 ℃～160 ℃, and polymerization reaction time is a dozens of minutes to 96 hour.
11. method as claimed in claim 10 is characterized in that, the polymerization temperature of employing is 60～140 ℃.
12. method as claimed in claim 10 is characterized in that, polymerization reaction time is 1 hour～72 hours.
13. the method for claim 1, it is characterized in that described Organohalogen compounds initiator is 2-methyl-2 bromopropionic acid ethyl ester, 2-bromo-butyric acid ethyl ester, 2-ethyl bromoacetate, 2 bromopropionic acid ethyl ester, 2-methyl-2-chloropropionate, 2-neoprene acid ethyl ester, 2-ethyl chloroacetate, ethyl trichloroacetate, 2-methyl-2 bromopropionic acid propyl ester, tetracol phenixin, benzyl chloride, bromotoluene, alpha-chloro ditane, alpha-brominated ditane, Triphenyl methane chloride 99, triphen monobromethane, p-methyl benzene sulfonic chloride, chlorallylene, allyl bromide 98 or its arbitrary combination.
14. the method for claim 1 is characterized in that, described catalyzer is Cu, Fe, CuCl, CuBr, FeCl
2, FeBr
2Or its arbitrary combination.
15. the method for claim 1, it is characterized in that described coordination agent is two (2-dimethyl amido ethyl) ethers, two (2-diethyl amido ethyl) ether, two (2-dibutyl amido ethyl) ether, two (2-dimethyl amido propyl group) ether or its arbitrary combination.
16. the method for claim 1 is characterized in that, described vinylbenzene and derivative thereof are vinyl toluene, ethyl styrene or alpha-methyl styrene.
17. the method for claim 1, it is characterized in that described acrylate and methacrylic ester are methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or its mixture.
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| DE10236133A1 (en) * | 2002-08-07 | 2004-02-26 | Byk-Chemie Gmbh | Use of gradient copolymers produced by living, controlled polymerization of ethylenically unsaturated monomers as dispersants, especially in coating compositions, pastes or molding materials |
| FR2848557B1 (en) * | 2002-12-13 | 2006-07-07 | Atofina | SOLUBLE OR AT LEAST DISPERSIBLE GRADIENT COPOLYMERS IN WATER AS IN ORGANIC SOLVENTS |
| JP2005002325A (en) * | 2003-05-19 | 2005-01-06 | Canon Inc | Polymer, polymer composition containing the same, ink composition, and method and apparatus for applying ink using the ink composition |
| FR2969158B1 (en) * | 2010-12-15 | 2013-01-18 | Arkema France | METHOD FOR CHOCY MODIFIERS AND SHOCK MODIFIED THERMOPLASTIC COMPOSITION HAVING IMPROVED HYDROLYTIC RESISTANCE |
| CN103205202A (en) * | 2013-04-03 | 2013-07-17 | 中山职业技术学院 | Gradient function coating with surface tension changed in gradient way and preparation method thereof |
| FR3025131B1 (en) * | 2014-09-03 | 2016-09-16 | Airbus Group Sas | PRE-POLYMERIZED THERMOSETTING COMPOSITE PIECE AND METHODS OF MAKING SUCH A PART |
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