CN1339514A - Process for preparing poly ether-polyolefine unsaturated compound block copolymer - Google Patents
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Abstract
The process for preparing unsaturated polyether-polyolefin block copolymer includes: the anionic polymerization of epoxy compound in the presence of alcoholate as initiator; the reaction of the obtained polymer with 2-halogen acyl halide; and the further active free radical polymerization of the obtained prepolymer containing 2-halogen acyl oxy radical terminal and unsaturated olefine compound in the presence of catalyst and complexing agent to produce unsaturated polyether-polyolefin block copolymer product. The block copolymer of the present invention may have clear molecular structure, optional length and ratio of the two blocks, narrow molecular weight distribution and relatively high purity.
Description
The invention belongs to the synthetic field of high molecular polymer.More particularly, the present invention relates to the preparation method of poly ether-polyolefine unsaturated compound block copolymer.
Recently, the work of the segmented copolymer that preparation is made up of hydrophilic and hydrophobic segment has caused people's very big interest, because it has the physicochemical property of uniqueness and to the susceptibility of medium, therefore in biological chemistry, biomedicine and intelligent material field, obtained using widely.Ethylene oxide and (methyl) alkyl-acrylates segmented copolymer family macromolecule multipolymer that comes to this.Many people once carried out research to the synthetic method and the physical and chemical performance of ethylene oxide and alkyl methacrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.They can effectively improve the consistency of incompatible system, can increase the stability of soliquid and micellar solution and dilute solution is had extremely strong thickening effect.They are the comparatively good expanding material of a kind of performance, tensio-active agent, also are the important source material of caking agent, coating, permeable membrane and thermoplastic elastomer etc.Its structural formula is as follows:
Wherein:
M
1It is the unit that is derived from epoxy compounds;
M
2It is the unit that is derived from alefinically unsaturated compounds;
N, m are respectively M
1And M
2Unitary number, n=10～2000, m=10～1000; R
1And R
2Be respectively hydrogen atom, Cl, Br or C
1-C
20Organic fatty family alkyl.
Be a typical example as polyethylene oxide-polymethylmethacrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, its structural formula is:
In the formula: n, m are same as above.
At present, many patents and document disclose the preparation method of these segmented copolymers, comparatively typically have:
1.M.Tomoi and Y.Shibayama is at polymkeric substance periodical (Polym J), 1976, the 6:190-195 report, under certain conditions, as under the lower temperature of tetrahydrofuran (THF) (THF) neutralization, the alcoxyl negatively charged ion of polyoxyethylene also can cause methyl methacrylate (MMA) polymerization effectively, obtains corresponding segmented copolymer (PEO-b-PMMA).But, the carrying out of this block copolymerization reaction will overcome following two difficulties at least: the solubleness of (1) PEO chain in some organic solvents commonly used such as THF, benzene and toluene is lower, carry out in order to guarantee that block copolymerization is reflected under the homogeneous condition, the temperature that causes the MMA reaction will be higher than 20 ℃ at least.But most alkyl methacrylate negatively charged ion are unsettled under this temperature, are very easy to take place chain transfer and chain termination reaction; (2) transesterification reaction taking place easily, therefore, often has graft copolymer to generate between PEO negatively charged ion and MMA monomer.
2. the honest and clean and Huang Xiaoyu of yellow fine horse is Chinese science (B collects), 1996,26 (6): 488～495 and Chinese science (B collects), 1997, open in 27 (6): 511～516 grades, be parent with para-aminophenol, by the continuous initiation of alcoxyl negatively charged ion and charge transfer complex, synthesized above-mentioned PEO-b-PMMA, but monomeric transformation efficiency is not high.
3. the quick and Qiu Kunyuan of Yang Xiao is at the polymer science periodical; unadulterated application chemistry (J.Macromol.Sci.; Pure Appl.Chem.); A34 (3); 543-549 (1997) has reported first synthetic α-dithio diethylin ethanoyl-ω-dithio diethylin acetoxyl group polyethylene oxide macromole iniferter agent, then in the light-initiated method of synthesizing polyether-polyene ethylenically unsaturated compounds triblock copolymer down.
4.Nair C.P.R. and Clouet G. are at the polymer science periodical, polymer chemistry physics summary (J.Macromol Sci., Rev.Macromol.Chem.Phys.), 1991, C31:311 and Nair C.P.R., Chaumout P and Clouet G. are at polymer science chemical periodical (J.Macromol.Sci.Chem.), 1990, A27 (6): 791 and people such as NairC.P.R. at polymer chemistry (Makromol.Chem.), 1991,1992 (3): 579 and Nair C.P.R., Clouet G. is at polymer (Macromolcules), 1990,23:1361 has reported and has utilized monohydroxy, two hydroxyl polyoxyethylene POE and piperazine or with the synthetic respectively two class macromole iniferter agents that obtain of dithiocarbonic anhydride, corresponding initiation styrene polymerization then obtains the method for A-B-A type triblock copolymer and segmented copolymer respectively, and the control certain molecular weight can obtain having the amphipathic multipolymer that replaces hydrophilic section and hydrophobic section.
5.Bamford C.H. and Middl eton J.P., at European polymkeric substance periodical (Er.Polvm.J.), 1987,19:269 reported utilize a series of terminal group for-OH ,-NH
2With the telechelic polymer of-COOH respectively with three chloro methyl isocyanate (O=C=NCCl
3) reaction, the formation terminal group is-CCl
3Polymkeric substance, under illumination condition, be that catalyzer is [as Mn then with the metal carbonyl
2(CO)
10] formation-CX
2Free radical and cause another alefinically unsaturated compounds polymerization forms the method for segmented copolymer.
There is obvious defects in the method for the synthesizing polyether of above-mentioned bibliographical information-polyene ethylenically unsaturated compounds segmented copolymer, is difficult to obtain the clear and purer segmented copolymer of molecular structure.And the open CN No.1166503A of Chinese patent application discloses a kind of method by existing hydroxyl or synthetic A (B) n (n 〉=2) the type multipolymer of amino-complex commodity, but synthetic molecules clear in structure, purer polyene ethylenically unsaturated compounds-poly ether-polyolefine unsaturated compound block copolymer that B segment molecule segmental length, ratio can be regulated arbitrarily, but the length of polyethers section (A) cannot be regulated arbitrarily.K.Jankova, in polymkeric substance communication (PolymerBulletin), 1999,42,153～159 have reported a kind of method by existing hydroxy-containing compounds commodity synthesizing polyether-poly-rare ethylenically unsaturated compounds segmented copolymer, but the length of same polyether block cannot be regulated arbitrarily.
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method for preparing poly ether-polyolefine unsaturated compound block copolymer is provided, the block copolymer clear in structure that this method makes, the chain length of polyethers and polyene ethylenically unsaturated compounds block part, ratio can be regulated arbitrarily, molecular weight distribution is narrower and purer, it is characterized in that (1) adopts the hydrocarbon oxy alkaline metal is initiator, and be to adopt the three-step approach synthetic, (2) chain length of two block parts of polyethers and polyene ethylenically unsaturated compounds, ratio can be regulated arbitrarily, and this method has the reaction conditions gentleness, the monomer advantage of wide range of application.
Therefore, the invention provides a kind of method for preparing poly ether-polyolefine unsaturated compound block copolymer, this method comprises:
(1) is initiator with the hydrocarbon oxy alkaline metal, makes epoxy compounds carry out anionoid polymerization, generate the polyether prepolymer that contains-oxyl basic metal end;
(2) make the reaction of described prepolymer and 2-halogen acyl halide, obtain containing the polyether prepolymer of 2-halo acyloxy end; With
(3) prepolymer with the described 2-of containing halo acyloxy end continues to carry out active free radical polymerization with alefinically unsaturated compounds in the presence of catalyzer and coordination agent, generates described poly ether-polyolefine unsaturated compound block copolymer.
Below illustrate in greater detail the present invention.
The step of the inventive method (1) is, is initiator with the hydrocarbon oxy alkaline metal, makes epoxy compounds carry out anionoid polymerization, generates the polyether segment that contains-oxyl basic metal end.
The epoxy compounds that can be used for the inventive method is the epoxy compounds that per molecule contains 2-10 carbon atom.Suitable epoxy compounds monomer for example is oxyethane, propylene oxide, butylene oxide ring etc. and any mixture thereof, and what particularly be suitable for is oxyethane, propylene oxide and composition thereof.
Any initiator commonly used when the hydrocarbon oxy alkaline metal initiator that can be used for the inventive method can be the epoxy compounds living anion polymerization.Basic metal is preferably potassium or sodium, and-oxyl is preferably alkoxyl group and aralkoxy.The specific examples of hydrocarbon oxy alkaline metal initiator comprises uncle's fourth oxygen potassium, uncle's fourth oxygen sodium, oxyethyl group potassium, Sodium Ethoxide, sodium methoxide, methoxyl group potassium, uncle's penta oxygen potassium, uncle's penta oxygen sodium, propoxy-potassium, propoxy-sodium, n-butoxy potassium, n-butoxy sodium, sec-butoxy potassium, sec-butoxy sodium, benzene oxyethyl group potassium, benzene Sodium Ethoxide, benzyloxy potassium and benzyloxy sodium etc.
As needs, the step of the inventive method (1) can be carried out in the presence of thinner (solvent).Requirement to the kind of described thinner is very not strict, is generally aromatic hydroxy compound and polar compound that per molecule contains 6-10 carbon atom, as benzene, toluene and tetrahydrofuran (THF) etc.The consumption of thinner generally makes monomer: thinner=100:(50～2000) (weight).
When using more than one monomers in step (1), monomer can once add, and also can gradation add.When adopting the mode that repeatedly adds, different monomers can be sequentially added into,, add propylene oxide for the second time as adding for the first time oxyethane, or the like.
The reactive polymer that step (1) obtains comprises polyethylene oxide, poly(propylene oxide), ethylene oxide-propylene oxide block copolymer, epoxy ethane-epoxy propane random copolymer etc.
The step of the inventive method (1) is carried out under the epoxy compounds anionoid polymerization condition of routine.But preferable reaction temperature is-35 ℃～100 ℃, more preferably-15 ℃～80 ℃, the preferred reaction time is 1～96 hour, more preferably 10～72 hours.
The step of the inventive method (2) is prepolymer and the reaction of 2-halogen acyl halide that above-mentioned steps (1) is obtained, and obtains containing the polyether prepolymer of 2-halo acyloxy end.Normally in the polymerization system that step (1) obtains, directly add the 2-halogen acyl halide, proceed acylation reaction, carry out step (2).
The general formula that can be used for the 2-halogen acyl halide of the inventive method is R
nCX
mThe compound of COX, in the formula: X is chlorine or bromine independently of each other, and the integer of m=1～3, R are hydrogen atom or C
1-C
20Organic fatty family alkyl, n=0-2.2-halogen acyl halide commonly used is chloro-acetyl chloride, three chloro Acetyl Chloride 98Min.s, 2-bromo isobutyl acylbromide, the positive butyryl bromide of 2-bromo, 2-bromo propionyl bromide, bromo acetyl bromide etc.
There is no particular restriction to the processing condition of the acylation reaction of step (2), but preferable reaction temperature is-15 ℃～100 ℃, and more preferably 10 ℃～80 ℃, the preferred reaction time is 0.1～24 hour, more preferably 1～10 hour.The mol ratio of polyether prepolymer and 2-halogen acyl halide is preferably 1～10.
As needs, reaction product can adopt conventional method to be purified, remove wherein alkali metal halide and excessive 2-halogen acyl halide etc., the polyether prepolymer after being purified, it is 200-80000 that described polyether prepolymer is analyzed number-average molecular weight with gel permeation chromatography.
The step of the inventive method (3) is that the polyether prepolymer that contains 2-halo acyloxy end that above-mentioned steps (2) obtains is continued to carry out living free radical polymerization with alefinically unsaturated compounds in the presence of catalyzer and coordination agent, to make poly ether-polyolefine unsaturated compound block copolymer.Normally above-mentioned polyether prepolymer is placed the reactor that contains catalyzer and coordination agent, add alefinically unsaturated compounds and carry out polymerization, promptly generate described poly ether-polyolefine unsaturated compound block copolymer.
The catalyzer that is suitable for is the halogenide of transition metal or transition metal, and specific examples comprises transition metal Cu, Fe or their halogenide, is preferably CuCl, CuBr, FeCl
2, FeBr
2And arbitrary combination.
The coordination agent that is suitable for is a nitrogenous compound, commonly used is 2,2 '-bipyridine or o-phenanthroline and derivative, Tetramethyl Ethylene Diamine and other many methyl polyamines and arbitrary combination thereof.
The alefinically unsaturated compounds that is suitable for is any vinyl monomer that contains two keys, monomer commonly used is a vinylbenzene, vinylformic acid, methacrylic acid, acrylate and methyl acrylic ester (for example methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, hydroxyethyl methylacrylate etc.), olefinically unsaturated nitriles class (for example vinyl cyanide etc.) and other can carry out the monomer of " activity " radical polymerization, and above-mentioned monomeric arbitrary combination.
There is no particular restriction to polymerization temperature that the inventive method step (3) adopts, but be generally-15 ℃～160 ℃, is preferably 20～140 ℃.Monomeric polymerization reaction time is not had special restriction yet, can be several minutes extremely about 96 hours, is generally preferred 1～65 hour 10 minutes～72 hours.The halogen in the prepolymer and the mol ratio of catalyzer are generally 0.1～3, and preferably 0.5～2; The mol ratio of catalyzer and coordination agent is generally 1～5, and preferably 1.5～4.
After reaction finished, available ordinary method reclaimed the segmented copolymer that forms.For example, with the product dissolution with solvents,, can repeat to obtain purified segmented copolymer for several times as needs subsequently with the precipitation agent precipitation.
The molecular weight of polyether block and polyene ethylenically unsaturated compounds block can be regulated arbitrarily in the segmented copolymer that the inventive method obtains, and has narrow molecular weight distribution.Generally speaking, the number-average molecular weight of polyether block is 200-80000, preferred 400-5000; The number-average molecular weight of polyene ethylenically unsaturated compounds block is 200-80000, preferred 400-5000.The overall number-average molecular weight of segmented copolymer is generally 400-160000, preferred 800-10000, and molecular weight distribution is 1.1-2.0, preferred 1.2-1.6.
Can find according to above disclosed technical scheme, the inventive method reaction conditions gentleness, raw material is easy to get, and is easy and simple to handle, and the monomer scope of application is wider, has good industrial prospect.
Below will the present invention is further illustrated by embodiment, but embodiment does not limit protection scope of the present invention.In these embodiments, molecular weight and molecular weight distribution be with Waters150-C equipment gel permeation chromatography, and with the polystyrene calibration of known molecular amount.
Embodiment 1
Through the baking of three pump drainages, charge at last in the reactor of high-purity argon and add 100 milliliters of tetrahydrofuran (THF)s and 20 gram oxyethane, cause with 2.08 mmole uncle fourth oxygen potassium, earlier 10 ℃ of following polymerizations 24 hours, and then be heated to 60 ℃ and reacted 48 hours.Add 4.5 milliliter of three chloro Acetyl Chloride 98Min. afterwards, reacted 10 hours down at 60 ℃.Question response finishes the back and precipitates with sherwood oil, filters, and vacuum-drying is dissolved again with benzene, and sherwood oil precipitates, filtration, drying, triplicate, and vacuum drying oven is dried to constant weight for 50～60 ℃.Promptly obtain containing the polyether prepolymer of 2-three chloro acyloxy ends, GPC records molecular weight Mn=2.54 * 10
3, MWD=1.18.
Weigh above-mentioned prepolymer 1 gram, with the chlorine atom in the prepolymer: cuprous chloride: 2,2 '-proportioning of bipyridine=1: 0.3: 1.5 (mol ratio) adds cuprous chloride 0.39 gram, bipyridine 0.28 gram, reinject 10 milliliters of dimethyl phthalates and 4.5 milliliters of butyl acrylates, reaction is 45 hours in 130 ℃ of oil baths.GPC surveys molecular weight, overall Mn=8.92 * 10 of segmented copolymer
3, MWD=1.46.
Embodiment 2
Make initiator with 19.1 mmole n-butoxy lithiums, 89 gram oxyethane are monomer, and 360 milliliters of tetrahydrofuran (THF)s are solvent; 38 mmole bromo acetyl bromides are acylating agent; all the other operations obtain containing the polyether prepolymer of 2-bromo acetoxyl group end with embodiment 1, and GPC records molecular weight Mn=4.04 * 10
3, MWD=1.13.
Weigh above-mentioned prepolymer 2 grams, with the bromine atoms in the prepolymer: cuprous bromide: the proportioning of phenylbenzene o-phenanthroline=1: 3: 6 (mol ratio) adds cuprous bromide 0.21 gram, phenylbenzene o-phenanthroline 0.86 gram, reinject 10 milliliters of phenyl ether and 5 milliliters of vinylbenzene, reaction is 10 hours in 140 ℃ of oil baths.GPC surveys molecular weight, overall Mn=1.14 * 10 of segmented copolymer
4, MWD=1.56.
Embodiment 3
Make initiator with 2.1 mmole uncle fourth oxygen potassium; 14 gram oxyethane are monomer; 100 milliliters of tetrahydrofuran (THF)s are solvent; 5 mmole bromo propionyl bromide are acylating agent; temperature of reaction is-15 ℃ and 80 ℃, and the reaction times is 48 hours and 24 hours, and all the other prescriptions and operation are with embodiment 1; obtain containing the polyether prepolymer (A) of 2-bromo propionyloxy end, GPC records molecular weight Mn=5.19 * 10
3, MWD=1.19.
Weigh above-mentioned prepolymer 4 grams, with the bromine atoms in the prepolymer: copper: 4,4-dinonyl-2,2 '-proportioning of bipyridine=1: 1: 2 (mol ratio) adds copper 0.049 gram, 4,4-dinonyl-2,2 '-bipyridine 0.445 gram, reinject 5 milliliters of dimethyl phthalates and 5 milliliters of methacrylic acid methyl, reaction is 20 hours in 80 ℃ of oil baths.GPC surveys molecular weight, overall Mn=8.94 * 10 of segmented copolymer
3, MWD=1.35.
Embodiment 4
Make initiator with 3.5 mmole uncle fourth oxygen sodium; 40 gram oxyethane are monomer; 150 milliliters of tetrahydrofuran (THF)s are solvent; 15 mmole 2-bromo isobutyl acylbromides are acylating agent; temperature of reaction is 0 ℃ and 40 ℃, and the reaction times is 48 hours and 48 hours, and all the other are with embodiment 1; promptly obtain containing the polyether prepolymer of 2-bromo isobutyl acyloxy end, GPC records molecular weight Mn=8.36 * 10
3, MWD=1.15.
Weigh above-mentioned prepolymer 3 grams, it with the mol ratio bromine atoms in the prepolymer: cuprous bromide: 2,2 '-proportioning of bipyridine=1: 1: 4 adds cuprous bromide 0.052 gram, 2,2 '-bipyridine 0.22 gram, reinject 5 milliliters of dimethyl phthalates and 1 milliliter of acetonitrile and 5 milliliters of methyl methacrylates, reaction is 65 hours in 20 ℃ of oil baths.GPC surveys molecular weight, overall Mn=1.52 * 10 of segmented copolymer
4, MWD=1.56.
Embodiment 5
Make initiator with 4 mmole uncles, penta oxygen potassium, 55 gram oxyethane are monomer, and 110 milliliters of tetrahydrofuran (THF)s are solvent; 8 mmole 2-bromo isobutyl acylbromides are acylating agent; all the other promptly obtain containing the polyether prepolymer of 2-bromo isobutyl acyloxy end with embodiment 1, and GPC records molecular weight Mn=1.12 * 10
4, MWD=1.15.
Weigh above-mentioned prepolymer 4 grams, with the mol ratio bromine atoms in the prepolymer: copper: cuprous bromide: 2,2 '-bipyridine=1: 2: 2: 6 proportioning adds copper 0.046 gram, cuprous bromide 0.102 gram, 2,2 '-bipyridine 0.33 gram, reinject 5 milliliters of dimethyl phthalates, 5 milliliters of dimethylbenzene and 10 milliliters of butyl methacrylate, reaction is 40 hours in 100 ℃ of oil baths.GPC surveys molecular weight, overall Mn=3.14 * 10 of segmented copolymer
4, MWD=1.64.
Embodiment 6
In the reactor identical, add 400 milliliters of benzene and 40 gram oxyethane and 10 gram propylene oxide with embodiment 1; make initiator with 10 mmole benzene Sodium Ethoxides; with 12 mmole 2-bromo isobutyl acylbromides is acylating agent; all the other are with embodiment 1; promptly obtain containing the polyether prepolymer of 2-bromo isobutyl acyloxy end; GPC surveys molecular weight, Mn=4.18 * 10
3, MWD=1.18.
Weigh above-mentioned prepolymer 2 grams, with the bromine atoms in the prepolymer: cuprous bromide: the proportioning of o-phenanthroline=1: 1.5: 4.5 (mol ratio) adds bromize alpha ketone 0.069 gram, o-phenanthroline 0.29 gram, reinject 5 milliliters of dimethyl phthalates and 5 milliliters of butyl acrylates, reaction is 45 hours in 130 ℃ of oil baths.GPC surveys molecular weight, overall Mn=1.18 * 10 of segmented copolymer
4, MWD=1.52.
Embodiment 7
Make initiator with 2 mmole uncles, penta oxygen sodium, 20 gram oxyethane are monomer, and 200 milliliters of tetrahydrofuran (THF)s are made solvent; 6 mmole 2-bromo isobutyl acylbromides are acylating agent; all the other promptly obtain containing the polyether prepolymer of 2-bromo isobutyl acyloxy end with embodiment 1, and GPC records molecular weight Mn=8.72 * 10
3, MWD=1.19.
Weigh above-mentioned prepolymer 4 grams, think the bromine atoms in the prepolymer: cuprous bromide: 2,2 '-proportioning of bipyridine=1: 2: 6 (mol ratio) adds cuprous bromide 0.065 gram, 2,2 '-bipyridine 0.22 gram, reinject 10 milliliters of dimethyl phthalates, 5 milliliters of vinylbenzene and 1 milliliter of vinyl cyanide, reaction is 35 hours in 80 ℃ of oil baths.GPC surveys molecular weight, overall Mn=1.72 * 10 of segmented copolymer
4, MWD=1.58.
Embodiment 8
In the reactor identical, add 100 milliliters of toluene, 100 milliliters of tetrahydrofuran (THF)s and 50 milliliters of oxyethane with embodiment 1, cause with 3 mmole Sodium Ethoxides, add 18 milliliters of chloro-acetyl chlorides afterwards, all the other are with embodiment 1, promptly obtain containing the polyether prepolymer of 2-chloro acyloxy end, GPC records molecular weight Mn=1.21 * 10
4, MWD=1.15.
Weigh above-mentioned prepolymer 5 grams, with the chlorine atom in the prepolymer: cuprous chloride: 2,2 '-proportioning of bipyridine=1: 1.5: 3 (mol ratio) adds cuprous chloride 0.061 gram, bipyridine 0.193 gram, reinject 20 milliliters of dimethyl phthalates and 20 milliliters of methyl acrylates, reaction is 62 hours in 130 ℃ of oil baths.GPC surveys molecular weight, overall Mn=3.82 * 10 of segmented copolymer
4, MWD=1.65.
Claims (9)
1. method for preparing poly ether-polyolefine unsaturated compound block copolymer, this method comprises:
(1) is initiator with the hydrocarbon oxy alkaline metal, makes epoxy compounds carry out anionic polymerisation, generate the polyether prepolymer that contains-oxyl basic metal end;
(2), obtain containing the polyether prepolymer of 2-halo acyloxy end with described prepolymer and the reaction of 2-halogen acyl halide; With
(3) prepolymer with the described 2-of containing halo acyloxy end continues to carry out active free radical polymerization with alefinically unsaturated compounds in the presence of catalyzer and coordination agent, generate poly ether-polyolefine unsaturated compound block copolymer, described catalyzer is transition metal or its halogenide, and described coordination agent is an organic compounds containing nitrogen.
2. according to the method for claim 1, it is characterized in that, described epoxy compounds is the epoxy compounds that per molecule contains 2-10 carbon atom, optimization ethylene oxide, propylene oxide, butylene oxide ring or its any mixture, most preferably oxyethane, propylene oxide or its mixture.
3. according to the method for claim 1 or 2, it is characterized in that described alefinically unsaturated compounds is vinylbenzene, vinylformic acid, methacrylic acid, acrylate, methacrylic ester, olefinically unsaturated nitriles or its any mixture.
4. according to each method among the claim 1-3, it is characterized in that described 2-halogen acyl halide is a general formula R
nCX
mCompound shown in the COX, in the formula, X is chlorine or bromine independently of each other, and m is the integer of 1-3, and R is hydrogen atom or or C
1-C
20Organic fatty family alkyl, n are 0～2 integer; Preferred chloro-acetyl chloride, three chloro Acetyl Chloride 98Min.s, 2-bromo isobutyl acylbromide, the positive butyryl bromide of 2-bromo, 2-bromo propionyl bromide, bromo acetyl bromide or its any mixture.
5. according to each method among the claim 1-4, it is characterized in that, described hydrocarbon oxy alkaline metal initiator is alkoxy base metal or aralkoxy basic metal, preferred tertiary fourth oxygen potassium, uncle's fourth oxygen sodium, oxyethyl group potassium, Sodium Ethoxide, sodium methoxide, methoxyl group potassium, uncle's penta oxygen potassium, uncle's penta oxygen sodium, propoxy-potassium, propoxy-sodium, positive fourth oxygen potassium, positive fourth oxygen sodium, Zhong Ding oxygen potassium, Zhong Ding oxygen sodium, benzene oxyethyl group potassium, benzene Sodium Ethoxide, benzyloxy potassium, benzyloxy sodium or its any mixture.
6. according to each method among the claim 1-5, it is characterized in that described catalyzer is Cu, Fe, CuCl, CuBr, FeCl
2, FeBr
2Or its any mixture.
7. according to each method among the claim 1-6, it is characterized in that, described coordination agent is 2,2 '-bipyridine or o-phenanthroline and derivative or their any mixture.
8. according to each method among the claim 1-7, it is characterized in that in step (3), the halogen in the described polyether prepolymer and the mol ratio of catalyzer be 0.1～3, preferred 0.5～2, the mol ratio of catalyzer and coordination agent is 1～5, preferred 1.5～4.
9. according to each method among the claim 1-8, it is characterized in that the temperature of reaction of step (1) is-35 ℃～100 ℃, preferred-15 ℃～80 ℃, the reaction times is 10 minutes～96 hours, preferred 1～72 hour; The temperature of reaction of step (2) is-15 ℃～100 ℃, preferred 10 ℃～80 ℃, and the reaction times is 0.1～24 hour, preferred 1～10 hour; The temperature of reaction of step (3) is-15 ℃～160 ℃, preferred 20 ℃～140 ℃, and the reaction times is 10 minutes～72 hours, preferred 1～65 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459612A (en) * | 2017-09-11 | 2017-12-12 | 四川大学 | A kind of activeness and quietness agent, epoxy resin toughened composite and preparation method thereof |
| CN108456581A (en) * | 2018-05-08 | 2018-08-28 | 四会市格鲁森润滑技术有限公司 | A kind of self-defoaming type copolyether lubricant and its manufacturing method |
-
2000
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459612A (en) * | 2017-09-11 | 2017-12-12 | 四川大学 | A kind of activeness and quietness agent, epoxy resin toughened composite and preparation method thereof |
| CN107459612B (en) * | 2017-09-11 | 2019-11-29 | 四川大学 | A kind of activeness and quietness agent, epoxy resin toughened composite material and preparation method |
| CN108456581A (en) * | 2018-05-08 | 2018-08-28 | 四会市格鲁森润滑技术有限公司 | A kind of self-defoaming type copolyether lubricant and its manufacturing method |
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