CN102516521B - Phenyl allyl alcohol polyether and preparation method thereof - Google Patents
Phenyl allyl alcohol polyether and preparation method thereof Download PDFInfo
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- CN102516521B CN102516521B CN 201110342931 CN201110342931A CN102516521B CN 102516521 B CN102516521 B CN 102516521B CN 201110342931 CN201110342931 CN 201110342931 CN 201110342931 A CN201110342931 A CN 201110342931A CN 102516521 B CN102516521 B CN 102516521B
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Abstract
The invention discloses phenyl allyl alcohol polyether and a preparation method thereof. The phenyl allyl alcohol polyether disclosed by the invention has an extremely good hydrophilic polyether structure and an extremely good oleophylic benzene ring structure; meanwhile, the amphipathic property of a branched chain can be adjusted and controlled as required; the phenyl allyl alcohol polyether can be taken as a polycarboxylic acid water reducing agent with excellent water reducing property and workability on concrete during macromonomer synthesis; and double bonds in a phenyl allyl alcohol polyether structure are conjugated with a benzene ring, so that the double bond activity of polyether is increased. The preparation method disclosed by the invention consists of two steps, and different types of required phenyl allyl alcohol polyether can be obtained simultaneously through a two-step reaction. The phenyl allyl alcohol polyether prepared with the method has good color and luster, the length of the branched chain is uniform, and the preparation method is simple, controllable and safe, and has a controllable process and stable reactions.
Description
Technical field
The invention belongs to the synthesis technical field of polyethers, be specifically related to a kind of phenyl propyl alcohol polyethers and preparation method thereof.
Background technology
In Concrete Industry, along with developing rapidly of concrete industry, in the urgent need to the workability of raising precast concrete and intensity and the weather resistance of concrete structure.The raising of workability and the minimizing of unit consumption of water are important problems, and each concrete admixture manufacturers all is being devoted to the exploitation of high-performance water reducing agent.Wherein high performance water reducing agent of polyocarboxy acid has extraordinary performance, high water reducing ability and workability that it has other water reducer such as naphthalene water reducer not to obtain.Yet its water-reducing property and workability still are inadequate.
In the technology of existing production polycarboxylate water-reducer, what affect the polycarboxylate water-reducer performance mainly is the structure of large monomer, and the large monomer for the production of polycarboxylate water-reducer mainly contains at present: polyoxyethylene glycol, poly glycol monomethyl ether, allyl polyglycol ether, methacrylic polyglycol ether, 3-methyl-3-butenyl polyethers, poly glycol monomethyl ether (methyl) acrylate etc.In order to improve the performance of polycarboxylate water-reducer, for example water reducing ability and workability are necessary to develop new large monomer, for the preparation of better polycarboxylate water-reducer.
Summary of the invention
The purpose of this invention is to provide a kind of phenyl allyl alcohol polyether and preparation method thereof, it can for the synthesis of polycarboxylate water-reducer, can give the workability of polycarboxylate water-reducer excellence as large monomer.
The structural formula of the phenyl allyl alcohol polyether of the present invention's preparation is as follows:
Wherein, C
2H
4O is oxyethylene group, C
3H
6O is oxypropylene group; M, n represent respectively the average addition mole number of oxyethylene group and oxypropylene group, and m, n are more than or equal to 0, the integer less than or equal to 100, and m, n are not 0 simultaneously; R is the alkyl of 0-5 carbon;
For the side chain of said structure formula, m and n are not 0 simultaneously, refer to that this side chain comprises that following 3 kinds of situation: m are at 0 o'clock, is the polyoxypropylene base; N is 0 o'clock, is polyoxyethylene groups; M and n are not 0 o'clock, are the mixing copolymerization chain of oxyethylene group and oxypropylene group.
Phenyl allyl alcohol polyether of the present invention adopts the method that is prepared as follows:
(1) in the stainless steel high-pressure reactor, adds phenyl allyl alcohol and catalyzer, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and under nitrogen atmosphere, be warming up to 40-180 ℃, under 50-200Kpa pressure, add epoxy alkane reaction 3.5-4.5h, the mol ratio of phenyl allyl alcohol and epoxy alkane is 1:2-1:75, then at 40-180 ℃ of lower insulation 2.5-3h epoxy alkane is reacted completely, then be cooled to 20-50 ℃, obtain the product phenyl allyl alcohol polyether;
(2) continue reactor is heated to 40-180 ℃ under nitrogen atmosphere behind the product phenyl allyl alcohol polyether of 10wt%-90wt% in the taking-up step (1), under 50-200Kpa pressure, add epoxy alkane reaction 5.5-6.5h, the mass ratio of surplus materials is 6302:1619 in the add-on of epoxy alkane and the reactor, at 40-180 ℃ of insulation 2.5-3.5h, epoxy alkane is reacted completely, be cooled to 20-60 ℃ of discharging, obtain phenyl allyl alcohol polyether.
The catalyzer that uses in the step (1) is the hydride of metallic lithium, the hydride of sodium, hydride, sodium methylate, sodium hydroxide or the potassium hydroxide of potassium.The usage quantity of catalyzer is the 0.05wt%-0.3wt% that adds epoxy alkane in the step (1).
Described epoxy alkane is one or both in oxyethane, the propylene oxide.
The structural formula of described phenyl allyl alcohol is as follows:
R wherein
1Alkyl for 0-5 carbon.
In above-mentioned steps (2), the preferred 110-140 of the temperature of reaction when adding separately raw material oxyethane or propylene oxide ℃.
The preferred 1:2-1:54 of mol ratio of phenyl allyl alcohol and epoxy alkane in the described step (1), thereby obtain the molecular weight minimum and be 200 and be 2400 target product to the maximum, be convenient to continue the addition epoxy alkane in the step (2), obtain the more single oxyalkylene group of macromolecule or the target product of mixed oxidization thiazolinyl.
Phenyl allyl alcohol polyether of the present invention is used for the synthetic of polycarboxylate water-reducer mainly as large monomer.The present invention has following advantage:
1, the phenyl allyl alcohol polyether of the present invention's acquisition has benzene ring structure, and the amphipathic property of side chain can be regulated and control as required simultaneously, can be used as the synthetic polycarboxylate water-reducer that concrete is had excellent water reducing ability and workability of large monomer;
2, in the phenyl allyl polyether structure that the present invention obtains, two keys and phenyl ring conjugation increase two key activity of polyethers, when polyethers and acrylic acid copolymer, the polyether reactant activity is higher than at present known polyethers, and the polyethers that the water reducer Disabled of preparation stays is less than known polyethers;
3, among the preparation method of the present invention, can obtain simultaneously the different phenyl allyl polyethers that need by step (1) and (2);
4, the phenyl allyl alcohol polyether good colour that adopts preparation method of the present invention to obtain, side chain length is even;
5, preparation method of the present invention is simple and practical, and technique is controlled, heats up under nitrogen atmosphere and reaction, can guarantee the steady and safety of reacting.
Embodiment
By following embodiment the present invention is made more detailed description, but should not limit protection scope of the present invention with this.In the following example, unless stated otherwise, " umber " refers to umber by mass.
Embodiment 1
(1) in the stainless steel high-pressure reactor, adds 1593 parts of 3-phenyl-2-propylene-1-alcohol and 9 parts of potassium hydride KHs, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and under nitrogen atmosphere, be warming up to 110 ± 5 ℃, keep 110 ℃, under 180KPa pressure, add 5117 parts of oxyethane, reaction 4h, then make reacting ethylene oxide complete at 110-120 ℃ of lower insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after BE-10), wherein ethyleneoxide addition is 10:1 to the average addition molar ratio of 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 40 ℃, takes out 5100 parts of BE-10;
(2) continue reactor is heated to 110 ℃ under nitrogen atmosphere behind 5100 parts of BE-10 of taking-up, keep 110 ℃, under 180KPa pressure, add 6302 parts of reacting ethylene oxide 6h, make reacting ethylene oxide complete at 110-120 ℃ of insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after BE-35), wherein ethyleneoxide addition is 35:1 to the average addition molar ratio of 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 55 ℃ of dischargings, gets 7910 parts of BE-35.
Embodiment 2
(1) in the stainless steel high-pressure reactor, adds 1593 parts of 2-phenyl vinyl carbinols and 9 parts of potassium hydride KHs, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and under nitrogen atmosphere, be warming up to 110 ± 5 ℃, keep 110 ℃, add 2600 parts of oxyethane at 150KPa, reaction 4h, then make reacting ethylene oxide complete at 110-120 ℃ of lower insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after ME-5), wherein on average have 5 moles of ethylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 30 ℃, takes out 2200 parts of ME-5;
(2) continue reactor is heated to 110 ℃ under nitrogen atmosphere behind 2200 parts of ME-5 of taking-up, keep 110 ℃, add 4907 parts of reacting ethylene oxide 6h at 150KPa, make reacting ethylene oxide complete at 110 ℃ of insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after ME-20), wherein on average have 25 moles of ethylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 55 ℃ of dischargings, gets 6900 parts of ME-20.
Embodiment 3
(1) in the stainless steel high-pressure reactor, adds 1593 parts of 3-phenyl-2-propylene-1-alcohol and 9 parts of potassium hydride KHs, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and be warming up to 110 ± 5 ℃ at nitrogen atmosphere, keep 110 ℃, add 6747 parts of propylene oxide at 100KPa, reaction 4h, then make propylene oxide reaction complete at 110-120 ℃ of lower insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after BP-10), wherein on average have 10 moles of propylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to below 50 ℃, takes out 6724 parts of BP-10;
(2) continue reactor is heated to 110 ℃ under nitrogen atmosphere behind 6724 parts of BP-10 of taking-up, keep 110 ℃, add 8310 parts of propylene oxide reaction 6h at 100KPa, make propylene oxide reaction complete at 110-120 ℃ of insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after BP-35), wherein on average have 35 moles of propylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 55 ℃ of dischargings, gets 9920 parts of BP-35.
Embodiment 4
(1) in the stainless steel high-pressure reactor, adds 1593 parts of 2-phenyl vinyl carbinols and 9 parts of potassium hydride KHs, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and be warming up to 110 ± 5 ℃ at nitrogen atmosphere, keep 110 ℃, add 10120 parts of propylene oxide at 80KPa, reaction 4h, then make propylene oxide reaction complete at 110-120 ℃ of lower insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after MP-15), wherein on average have 15 moles of propylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to below 50 ℃, takes out 6907 parts of BP-15;
(2) continue reactor is heated to 110 ℃ under nitrogen atmosphere behind 6907 parts of BP-15 of taking-up, keep 110 ℃, add 5657 parts of propylene oxide reaction 6h at 80KPa, make propylene oxide reaction complete at 110-120 ℃ of insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after MP-20), wherein on average have 35 moles of propylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 55 ℃ of dischargings, gets 10463 parts of BP-35.
Embodiment 5
(1) in the stainless steel high-pressure reactor, adds 1593 parts of 3-phenyl-2-propylene-1-alcohol and 9 parts of potassium hydride KHs, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and be warming up to 110 ± 5 ℃ at nitrogen atmosphere, keep 110 ℃, add 15686 parts of oxyethane at 50KPa, reaction 4h, then make reacting ethylene oxide complete at 110-120 ℃ of lower insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after BE-30), wherein on average have 15 moles of ethylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to below 50 ℃, takes out 11714 parts of BE-30;
(2) continue reactor is heated to 110 ℃ under nitrogen atmosphere behind 11714 parts of BE-30 of taking-up, keep 110 ℃, add 4495 parts of propylene oxide reaction 6h at 50KPa, make propylene oxide reaction complete at 110-120 ℃ of insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after BEP-20), wherein on average have 20 moles of propylene oxide of 15 moles of ethylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 55 ℃ of dischargings, gets 10060 parts of BEP-20.
Embodiment 6
(1) in the stainless steel high-pressure reactor, adds 1593 parts of 2-phenyl vinyl carbinols and 9 parts of potassium hydride KHs, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and be warming up to 110 ± 5 ℃ at nitrogen atmosphere, keep 110 ℃, add 4183 parts of oxyethane at 200KPa, reaction 4h, then make reacting ethylene oxide complete at 110-120 ℃ of lower insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after BE-8), wherein on average have 8 moles of ethylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to below 50 ℃, takes out 2433 parts of BP-10;
(2) continue reactor is heated to 110 ℃ under nitrogen atmosphere behind 2433 parts of BP-10 of taking-up, keep 110 ℃, add 7182 parts of propylene oxide reaction 6h at 200KPa, make propylene oxide reaction complete at 110-120 ℃ of insulation 3h, thereby obtain a kind of phenyl allyl polyether (called after MEP-18), wherein on average have 18 moles of propylene oxide of 8 moles of ethylene oxide to add to 3-phenyl-2-propylene-1-alcohol; Then, reactor is cooled to 55 ℃ of dischargings, gets 10525 parts of MEP-18.
Claims (6)
1. a phenyl allyl alcohol polyether is characterized in that, its structural formula is as follows:
Wherein, C
2H
4O is oxyethylene group, C
3H
6O is oxypropylene group; M, n represent respectively the average addition mole number of oxyethylene group and oxypropylene group, and m, n are more than or equal to 0, the integer less than or equal to 100, and m, n are not 0 simultaneously; R is the alkyl of 0-5 carbon;
For the side chain of said structure formula, m and n are not 0 simultaneously, refer to that this side chain comprises that following 3 kinds of situation: m are at 0 o'clock, is the polyoxypropylene base; N is 0 o'clock, is polyoxyethylene groups; M and n are not 0 o'clock, are the mixing copolymerization chain of oxyethylene group and oxypropylene group.
2. the preparation method of a kind of phenyl allyl alcohol polyether according to claim 1 is characterized in that, its concrete preparation process is:
(1) in the stainless steel high-pressure reactor, adds phenyl allyl alcohol and catalyzer, thermometer, agitator and nitrogen ingress pipe are installed on the stainless steel reactor; Start under the logical nitrogen gas stirring of outer circulation and take air in the reactor out of, and under nitrogen atmosphere, be warming up to 40-180 ℃, under 50-200Kpa pressure, add epoxy alkane reaction 3.5-4.5h, the mol ratio of phenyl allyl alcohol and epoxy alkane is 1:2-1:75, then at 40-180 ℃ of lower insulation 2.5-3h epoxy alkane is reacted completely, then be cooled to 20-50 ℃, obtain the product phenyl allyl alcohol polyether;
(2) continue reactor is heated to 40-180 ℃ under nitrogen atmosphere behind the product phenyl allyl alcohol polyether of 10wt%-90wt% in the taking-up step (1), under 50-200Kpa pressure, add epoxy alkane reaction 5.5-6.5h, the mass ratio of surplus materials is 6302:1619 in the add-on of epoxy alkane and the reactor, at 40-180 ℃ of insulation 2.5-3.5h, epoxy alkane is reacted completely, be cooled to 20-60 ℃ of discharging, obtain phenyl allyl alcohol polyether.
3. preparation method according to claim 2 is characterized in that, the catalyzer described in the step (1) is the hydride of metallic lithium, the hydride of sodium, hydride, sodium methylate, sodium hydroxide or the potassium hydroxide of potassium; The usage quantity of catalyzer is the 0.05wt%-0.3wt% that adds epoxy alkane in the step (1).
4. according to claim 2 or 3 described preparation methods, it is characterized in that described epoxy alkane is one or both in oxyethane, the propylene oxide.
5. preparation method according to claim 2 is characterized in that, the structural formula of described phenyl allyl alcohol is as follows:
R wherein
1Alkyl for 0-5 carbon.
6. preparation method according to claim 4 is characterized in that, the temperature of reaction when adding raw material oxyethane or propylene oxide separately in the step (2) is 110-140 ℃.
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| CN104292451A (en) * | 2014-10-15 | 2015-01-21 | 南京红宝丽股份有限公司 | Preparation method and application of unsaturated polyether |
| CN106893048B (en) * | 2017-04-10 | 2019-04-02 | 上海台界化工有限公司 | A kind of preparation method of polycarboxylic acids dehydragent |
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| JP2009242611A (en) * | 2008-03-31 | 2009-10-22 | Nof Corp | Copolymer production method |
| CN101724145A (en) * | 2008-01-14 | 2010-06-09 | 张建荣 | Preparation method of macromolecular monomer of copolymeric polycarboxylic acid water reducing agent |
| CN102115516A (en) * | 2010-12-22 | 2011-07-06 | 江苏博特新材料有限公司 | Preparation method for comb-shaped copolymer cement dispersant, monomer used therein and prepared comb-shaped copolymer cement dispersant |
| CN102146159A (en) * | 2010-11-24 | 2011-08-10 | 辽宁奥克化学股份有限公司 | Vinyl polyether and preparation method and application thereof |
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| CN101724145A (en) * | 2008-01-14 | 2010-06-09 | 张建荣 | Preparation method of macromolecular monomer of copolymeric polycarboxylic acid water reducing agent |
| JP2009242611A (en) * | 2008-03-31 | 2009-10-22 | Nof Corp | Copolymer production method |
| CN102146159A (en) * | 2010-11-24 | 2011-08-10 | 辽宁奥克化学股份有限公司 | Vinyl polyether and preparation method and application thereof |
| CN102115516A (en) * | 2010-12-22 | 2011-07-06 | 江苏博特新材料有限公司 | Preparation method for comb-shaped copolymer cement dispersant, monomer used therein and prepared comb-shaped copolymer cement dispersant |
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