CN104193985A - Preparation method of esterified macromer for polycarboxylate water-reducer - Google Patents
Preparation method of esterified macromer for polycarboxylate water-reducer Download PDFInfo
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Abstract
The invention provides a preparation method of an esterified macromer for a polycarboxylate water-reducer. The preparation method comprises the following steps: performing carboxylation reaction on terminal hydroxyl of mono-hydroxyl-terminated polyether to obtain a polyether intermediate with carboxylate as a terminal group; performing esterification reaction on the polyether intermediate with carboxylate as the terminal group to obtain the esterified macromer for the polycarboxylate water-reducer. According to the method, an organic solvent does not need to be used as a water-carrying agent, the reaction condition is mild, side reactions are few, and the polymerizable activity of the obtained esterified macromer is high; the method is an efficient and environment-friendly novel method for preparing the esterified macromer for the polycarboxylate water-reducer.
Description
Technical field
The invention belongs to the preparation field of ester compound, specifically the preparation method of the large monomer of esterification for a kind of polycarboxylate water-reducer.
Technical background
Polycarboxylate water-reducer is a kind of by the synthetic polymkeric substance with certain molecular weight of acrylic acid or the like, the large monomer of polyethers and other monomer copolymerizations.Due to it, there is the advantages such as high water reducing rate, high slump retaining, mobility hold facility are good, low-dosage, in the construction projects such as water power, highway, nuclear power and high ferro, use in a large number.Along with the construction of high-rise building, high residential building, large stadium etc., civilian commerical ready-mixed concrete is growing to the demand of polycarboxylate water-reducer.
The large monomer of esterification is as one of conventional large monomer of copolyether of polycarboxylate water-reducer, and in its structure, containing polymerisable unsaturated double-bond and take provides the sterically hindered master's of being polyether segment.Performance to polycarboxylate water-reducer has material impact.Building-up process to the large monomer of esterification is optimized, and the synthetic large monomer of esterification with better quality, is focus and the difficult point of current polycarboxylate water-reducer area research.
Ma Baoguo etc. (inquire into by the synthesizing method of monomer of polycarboxylic type water-reducer, Chinese building material science and technology .2007, (2), 50-52) synthetic method of ester type polyethers is concluded and arranged, method industrial and the synthetic ester type polyethers in academic research field is more with direct esterification at present.
Patent CN102746507A be take direct esterification as synthetic method, and take acrylic acid or the like, poly glycol monomethyl ether is raw material, and under 90-130 ℃ of condition, reaction 6-10h, has synthesized the higher large monomer of esterification of esterification yield.
Patent CN102504232A be take direct esterification as synthetic method, and take methylene-succinic acid, poly glycol monomethyl ether is raw material, and under 80-120 ℃ of condition, reaction 4-8h, has synthesized the higher large monomer of esterification of esterification yield.
Patent CN101125743 be take direct esterification as synthetic method, take poly glycol monomethyl ether or polyoxyethylene glycol, acrylic acid or the like is raw material, under 110-140 ℃ of condition, reaction about 5h, has synthesized esterification yield higher and can store for a long time the large monomer of stay-in-grade esterification.
Patent CN101041570 be take direct esterification as synthetic method, and take acrylic acid or the like, poly glycol monomethyl ether is raw material, and under 95-130 ℃ of condition, reaction 3.5-5.5h, has synthesized the higher large monomer of esterification of esterification yield.
(methacrylic acid (gathering) the glycol ether monoesters synthesising process research [D] such as Lei Haiqin, 2009.) take direct esterification as research method, system the factors such as the catalyzer of the esterification process of poly glycol monomethyl ether and methacrylic acid, esterification temperature and esterification time are studied and are optimized.The reaction conditions of optimizing is: temperature of reaction is 122 ℃, and the reaction times is 6h, has obtained the high large monomer of esterification of esterification yield.
The method of the synthetic large monomer of esterification of direct esterification is simple, by changing the reaction influence factors such as enzymatic synthesis condition and feed ratio, can access the large monomer of esterification that esterification yield is higher, is current industrial main method.But the weak point of this method is reaction needed, at higher temperature, carry out, because acrylic acid or the like is the more active monomer of a class, the side reactions such as autohemagglutination easily at high temperature occur, cause the large monomer of partial esterification not there is polymerization activity.
Summary of the invention
Direct esterification as the higher synthetic polycarboxylate water-reducer of esterification efficiency with the large monomer of esterification, it,, because temperature of reaction is higher, causes side reaction more, and the large monomer of esterification therefore obtaining has problems such as not possessing polymerization activity.The invention provides a kind of reaction process does not need to use band aqua, the method for the large monomer of synthetic esterification that esterification yield and two key retention rate are high.
Technical scheme: the present invention is to provide the preparation method of the large monomer of esterification for a kind of polycarboxylate water-reducer, comprise the following steps:
1) the carboxylic acid salinization of the terminal hydroxy group of one-ended hydroxy polyethers reaction: at 100-180 ℃, one-ended hydroxy polyethers reacts under catalyzer existence condition with acid anhydrides, after reaction 1-10h, in reaction system, add small molecular alcohol, insulation continues reaction 1-3h, and the reaction pressure of previous reaction is reaction system self pressure; Rear decompression vacuum pumping is removed volatile matter, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxyl.Utilize the polyether intermediate that alkaline reagents is carboxyl by above-mentioned end group to neutralize neutrality, the polyether intermediate that formation end group is carboxylate salt;
In described reaction, the mol ratio of one-ended hydroxy polyethers and acid anhydrides is 1:(1-3); The add-on of small molecular alcohol is to compare the molar weight of the acid anhydrides that one-ended hydroxy polyethers adds; The usage quantity of alkaline reagents be take reaction system and is reached PH and be as the criterion as neutrality;
Described one-ended hydroxy polyethers under the effect of catalyzer, carries out ring-opening polymerization preparation to epoxy alkane by initiator, and preparation method and catalyzer are known by this professional domain practitioner, and therefore not to repeat here.Wherein, initiator is one-ended hydroxy alcohol, and one-ended hydroxy alcohol is prepared one-ended hydroxy polyethers as initiator to epoxy alkane ring opening polymerization, and the alkyl segment of one-ended hydroxy alcohol is the end alkyl group of one-ended hydroxy polyethers.Polymerization is one or several in oxyethane, propylene oxide, tetrahydrofuran (THF), epoxy cyclohexane or glycidyl ether with epoxy alkane.
2) esterification of the polyether intermediate that end group is carboxylate salt: at 80-150 ℃, the polyether intermediate that is carboxylate salt by the end group of step (1) gained adds reactor together with unsaturated halogenating agent, under catalyst action, react 1-10h, keep temperature of reaction decompression vacuum pumping to remove volatile matter, remove by filter insoluble substance, obtain the large monomer of pure esterification;
In the described esterification of step (2), the polyether intermediate that end group is carboxylate salt and the mol ratio of unsaturated halogenating agent are 1:(1.1-10); Catalyzer usage quantity is for initially to add between the 1%-5% of end hydroxy polyether quality.
The large monomer of gained esterification has unsaturated double-bond and following feature structure:
Wherein, R is the alkyl segment in the initiator structure of one-ended hydroxy polyethers described in step (1), R
1and R
2representing the group in unsaturated halogenating agent structure described in step (1), is H atom or alkyl segment.
Catalysts described in step (1) is homogeneous phase or the heterogeneous catalyst such as the vitriol oil, tosic acid, ortho phosphorous acid, strong acidic ion resin NKC-9, Lewis acid, solid acid, heteropolyacid.The usage quantity of catalyzer is the 1%-5% of polyethers quality.
Described in step (1), one-ended hydroxy polyethers has following structure:
its number-average molecular weight is between 200-10000.
Described in step (1) in the structure of one-ended hydroxy polyethers:
The initiator that R is corresponding is the alkyl segment of the one-ended hydroxy alcohol between carbon atom number 1-20, and what belong to this class alcohol has straight chain, side chain, naphthenic hydrocarbon, heterocycle or aromatic series single hydroxyl alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 1-amylalcohol, 2-amylalcohol, hexalin, phenylcarbinol, 1-octanol, isooctyl alcohol, furans-3-methyl alcohol, triethyl silicane alcohol, 1-decanol, 1-undecyl alcohol, 1-stearyl alcohol.Select the carbon atom number of initiator and the difference of carbon-chain structure, can regulate the hydrophilic and oleophilic performance of the one-ended hydroxy polyethers of preparing, thereby meet the user demand of different application occasion.
End group radicals R base in described one-ended hydroxy polyether structure is finally retained in the poly carboxylic acid of synthesized with in the large monomer of esterification, and this R base is identical with the R base in the large monomer structure of esterification with described poly carboxylic acid
The monomer corresponding to structural unit of A representative is oxyethane, and what a represented is the polymerization degree of oxirane monomers, and numerical value is between 0-220;
The monomer corresponding to structural unit of B representative is propylene oxide, and what b represented is the polymerization degree of propylene oxide monomer, and numerical value is between 0-170;
The monomer corresponding to structural unit of C representative is tetrahydrofuran (THF), and what c represented is the polymerization degree of tetrahydrofuran monomers, and numerical value is between 0-130;
The monomer corresponding to structural unit of D representative is epoxy cyclohexane, and what d represented is the polymerization degree of epoxy cyclohexane monomer, and numerical value is between 0-100.
The monomer corresponding to structural unit of E representative is glycidyl ether, and monomer whose structural formula is
r wherein
3in group, include one or several in alkyl group, naphthenic hydrocarbon group, phenyl ring group, heterocyclic group, siloxanes group.What e represented is the polymerization degree of Racemic glycidol ether monomer, and numerical value is between 0-20.
The ethyl ether that has that belongs to this glycidyl ether, isopropyl glycidyl ether, glycidyl isobutyl ether, tertiary butyl glycidyl ether, butylglycidyl ether, octyl glycidyl ether, lauryl diglycidyl ether, tetradecyl glycidyl ether, glycidyl cetyl ether, 2-toluene glycidyl ether, benzyl glycidyl ether, 1, 2-epoxy-3-phenoxypropane, 4-methoxyphenyl glycidyl ether, 4-nonyl benzene glycidyl ether, Racemic glycidol furfuryl ether, 3-glycidyl ether oxygen base propyl trimethoxy silicane, (3-glycidoxy propyl group) dimethylethoxysilane, 3-[(2, 3)-epoxy the third oxygen] propyl group methyl dimethoxysilane, diethoxymethyl [(3-Oxyranyle methoxy) propyl group] silane, 3-glycidyl ether oxygen base propyl-triethoxysilicane etc.
The synthetic method of the polyethers of one-ended hydroxy described in technical scheme, by this professional domain, practitioner is known, and therefore not to repeat here.
Acid anhydrides described in step (1) is not contain the cyclic acid anhydride of polymerisable pair of key or triple bond.
The described acid anhydrides of step (1) is selected from Succinic anhydried, Tetra hydro Phthalic anhydride, biphenyl acid anhydrides, methane amide succinyl oxide, succinyl oxide, methylsuccinic acid acid anhydride, 2, 2-dimethyl succinic anhydride, phenylsuccinic acid acid anhydride, 2, 3-pyridine dicarboxylic acid acid anhydride, pyridine-3, 4-dicarboxylic anhydride, Pyroglutaric acid, 2-phenyl Pyroglutaric acid, 3-methylglutaric acid acid anhydride, 2, 2-dimethylated pentanedioic acid acid anhydride, 3, 3-dimethylated pentanedioic acid acid anhydride, 3, 3-tetramethylene Pyroglutaric acid, 3-(tertiary butyl dimethyl Si base) Pyroglutaric acid, 3-oxaspiro [5, 5] undecane-2, 4-diketone, 1, 2-cyclohexyl dicarboxylic acid acid anhydride, 1, 8-naphthalene dicarboxylic anhydride, 3-nitro-1, 8-naphthalic anhydride, 4-amino-1, 8-naphthalic anhydride, NA-acid anhydrides, N-methyl-isatin acid anhydrides, N-Z-L-aspartic anhydride etc.
Described in step (1), small molecular alcohol is single hydroxyl alcohol.The object that adds small molecular alcohol is to react away unnecessary cyclic acid anhydride, and generation one end is carboxylicesters, the compound that the other end is carboxylic acid.Prevent that remaining cyclic acid anhydride from forming dicarboxylate in N-process, in follow-up esterification, form the esterification material containing two unsaturated double-bonds.Because containing the esterification material of two unsaturated link(age)s, easily cause in synthetic polycarboxylate water-reducer process of later stage and occur partial cross-linked reaction, affect the performance of polycarboxylate water-reducer.
Described in step (1), the carbon atom of small molecular alcohol is between 1-20, and carbon-chain structure comprises one or several in the groups such as straight chain, side chain, naphthenic hydrocarbon, aromatic series, heterocycle.
Step 1) described small molecular alcohol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, hexalin, primary isoamyl alcohol, 1-heptanol, isooctyl alcohol, 1-lauryl alcohol, 1-stearyl alcohol, phenylcarbinol, triethyl silicane alcohol, tetrahydrochysene-3-furfuralcohol, furans-3-methyl alcohol etc.
Described in step (1), reactive end hydroxy polyethers does not have water generates with reacting of cyclic acid anhydride, may seldom a part of acid anhydrides after esterification open loop, do not have the carboxyl of esterification can continuation and polyethers or small molecular alcohol again there is esterification and produce water, but the generation of water seldom, for esterification itself, there is no king-sized impact.So can select not use band aqua in the reacting of end hydroxy polyether and acid anhydrides, this is a technical advantage in the present invention.
Described in step (1), alkaline reagents is Na
2cO
3, NaHCO
3, K
2cO
3, KHCO
3, MgCO
3, CaCO
3, Ca (HCO
3)
2liOH, NaOH, KOH, Mg (OH)
2, Al (OH)
3, Ca (OH)
2, one or several the mixture in ammonia, quadrol, propylene diamine, triethylamine etc.
In step (2), add into unsaturated halohydrocarbon there is on the one hand the effect that promotes that esterification yield improves, also can be used as in addition reaction solvent, reduce the viscosity of reaction mixture.After reaction finishes, unreacted unsaturated halohydrocarbon is used as esterifying reagent after can reducing pressure and steaming collection again.
Unsaturated halogenating agent described in step (2) can be described as the unsaturated halohydrocarbon containing unsaturated double-bond and haloid element, in its structure, carbon atom number is between 3-20, comprises one or several in the groups such as straight chain group, branched group, naphthenic hydrocarbon group, aromatic group, heterocyclic group in carbon-chain structure.
The described unsaturated halogenating agent of step (2) is selected from chlorallylene, 1-chlorine-2-methyl-1-propylene, methallyl chloride, allyl bromide 98, the bromo-2-methyl-1-propylene of 1-, methacrylic bromine, 1,3,2-CMB, bromo-3 methyl-2-butenes of 1-, the chloro-1-butylene of 3-, 3, 3-dimethyl-allyl bromine, allyl iodide, the chloro-1-cyclopentenes of 1-, 2-(chloromethyl) allyl group-trimethyl silane, 2-chloroacrylonitrile, 2-bromopropylene nitrile, methacrylic iodine, the chloro-1-hexene of 6-, the bromo-1-octene of 8-, the bromo-1-decene of 10-, the chloro-1-undecylene of 11-, the bromo-1-undecylene of 11-, cinnamyl chloride, the bromo-1-phenyl-1-of 3-propylene, 4-1-chloro-4-methyl-benzene etc.
Described in step (2), catalyzer is phase-transfer catalyst, be selected from triethylamine, methyl trioctylphosphine brometo de amonio, triethyl methyl brometo de amonio, tributyl-methyl phosphonium brometo de amonio, tetrabutylammonium chloride, Tetrabutyl amonium bromide, etamon chloride, phenyl trimethylammonium bromide, phenyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium Neutral ammonium fluoride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyltriethylammonium bromide, octadecyl trimethyl ammonium chloride, myristyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate etc.
Phase-transfer catalyst described in step (2) can be also the immobilized resin that has quaternary ammonium salt, and it is separated with reaction mass that the advantage of use quaternary ammonium resin is that catalyzer is easy to, thereby reaches the effect of catalyzer recycling.The quaternary ammonium resin with phase-transfer catalyst function comprises D201, D261, D280, D290, D296, D301R, D301G, D370, D392 etc.
Described in step (2) in esterification, the stability of unsaturated halogenating agent is higher, end group is stable chemical nature under the polyether intermediate High Temperature High Pressure of carboxylate salt, thus do not need to use stopper, thus reduce the stopper disadvantageous effect synthetic to follow-up polycarboxylate water-reducer.
In the present invention, the synthesis step of the large monomer of esterification can be described as: one-ended hydroxy polyethers, acid anhydrides, catalyzer are added in enclosed high pressure reactor according to a certain percentage, be warmed up to assigned temperature, insulation reaction is after for some time, add and the equimolar small molecular alcohol of residue acid anhydrides amount, continue insulation reaction for some time, add alkaline reagents to be neutralized to neutrality, decompression vacuum pumping is removed volatile matter, remove by filter insoluble substance, obtain the polyether intermediate that end group is carboxylate salt.
A certain amount of unsaturated halogenating agent and catalyzer are joined in polyether intermediate, be warming up to design temperature insulation reaction for some time, the unsaturated halogenating agent that reclaim under reduced pressure unreacted is complete, leftover materials remove by filter insoluble substance, obtain the large monomer of esterification.
The method of the invention, do not need with an organic solvent conduct band aqua, and reaction conditions is gentle, and side reaction is few, and the large monomer polymerizable of the esterification activity of acquisition is high, is a kind of novel method of the large monomer of esterification for polycarboxylate water-reducer of preparing of high-efficiency environment friendly.
Embodiment
Below by example, describe the present invention in detail, these examples are only illustrative, do not represent the restriction scope of application of the present invention, and in embodiment, medicine used or reagent all can buy by usual channel.
Embodiment 1
One-ended hydroxy polyethers, synthetic initiator is methyl alcohol, and polymerization single polymerization monomer is oxyethane and Racemic glycidol furfuryl ether, and the polymerization degree of oxyethane is 5, and the polymerization degree of Racemic glycidol furfuryl ether is 2, number-average molecular weight is 560g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1:0, and the consumption of catalyzer is 0% of polyethers quality.Take one-ended hydroxy polyethers 1mol (560g), Succinic anhydried 1mol, above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 100 ℃, insulation reaction 1h.In reaction system, add NaOH to be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:1, and catalyst levels is 1% of one-ended hydroxy polyethers quality.Take chlorallylene 1mol, catalyzer triethyl methyl brometo de amonio 5.60g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 80 ℃, insulation reaction 1h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 93.4%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 87.5%, and two key retention rates are 99.2%.
Embodiment 2
One-ended hydroxy polyethers, synthetic initiator is ethanol, and polymerization single polymerization monomer is epoxy cyclohexane, and the polymerization degree is 20, and number-average molecular weight is 2006g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1.05:0.05, and the consumption of catalyzer is 1% of polyethers quality.Take one-ended hydroxy polyethers 1mol (2006g), Tetra hydro Phthalic anhydride 1.05mol, catalyzer tosic acid 20.06g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 110 ℃, insulation reaction 2h.Then in reactor, add methyl alcohol 0.05mol, insulation continues reaction 1h.In reaction system, add KOH to be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:2, and catalyst levels is 1.5% of one-ended hydroxy polyethers quality.Take methallyl chloride 2mol, catalyzer methyl trioctylphosphine brometo de amonio 30.09g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 105 ℃, insulation reaction 2.5h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 94.2%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 89.5%, and two key retention rates are 99.4%.
Embodiment 3
One-ended hydroxy polyethers, synthetic initiator is 1-propyl alcohol, and polymerization single polymerization monomer is propylene oxide, and the polymerization degree is 30, and number-average molecular weight is 1800g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1.1:0.1, and the consumption of catalyzer is 1.2% of polyethers quality.Take one-ended hydroxy polyethers 1mol (1800g), methane amide succinyl oxide 1.1mol, catalyzer tosic acid 21.6g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 120 ℃, insulation reaction 2.2h.Then in reactor, add 1-propyl alcohol 0.1mol, insulation continues reaction 1.5h.In reaction system, add LiOH to be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:3, and catalyst levels is 1.75% of one-ended hydroxy polyethers quality.Take the bromo-2-methyl-1-propylene of 1-3mol, catalyzer tetrabutylammonium chloride 31.5g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 120 ℃, insulation reaction 3h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 94.7%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 90.2%, and two key retention rates are 99.6%.
Embodiment 4
One-ended hydroxy polyethers, synthetic initiator is 2-propyl alcohol, and polymerization single polymerization monomer is tetrahydrofuran (THF), and the polymerization degree is 40, and number-average molecular weight is 2940g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1.2:0.2, and the consumption of catalyzer is 1.5% of polyethers quality.Take one-ended hydroxy polyethers 1mol (2940g), methylsuccinic acid acid anhydride 1.2mol, catalyzer vitriol oil 44.1g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 130 ℃, insulation reaction 3.0h.Then in reactor, add primary isoamyl alcohol 0.2mol, insulation continues reaction 1.8h.In reaction system, add Na
2cO
3be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:4, and catalyst levels is 1.9% of one-ended hydroxy polyethers quality.Take 1,3,2-CMB 4mol, catalyzer phenyl trimethyl ammonium chloride 55.86g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 125 ℃, insulation reaction 4h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 95.2%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 93.2%, and two key retention rates are 99.7%.
Embodiment 5
One-ended hydroxy polyethers, synthetic initiator is n-butyl alcohol, and polymerization single polymerization monomer is propylene oxide and tetrahydrofuran (THF), and the polymerization degree of propylene oxide is 20, and the polymerization degree of tetrahydrofuran (THF) is 20, number-average molecular weight is 2674g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1.5:0.5, and the consumption of catalyzer is 1.7% of polyethers quality.Take one-ended hydroxy polyethers 1mol (2674g), Pyroglutaric acid 1.5mol, catalyzer vitriol oil 45.46g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 140 ℃, insulation reaction 5h.Then in reactor, add trimethyl carbinol 0.5mol, insulation continues reaction 2.0h.In reaction system, add NaHCO
3be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:5, and catalyst levels is 2.0% of one-ended hydroxy polyethers quality.Take the chloro-1-butylene 5mol of 3-, catalyzer Trimethyllaurylammonium bromide 53.48g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 130 ℃, insulation reaction 5h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 95.7%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 95.3%, and two key retention rates are 99.5%.
Embodiment 6
One-ended hydroxy polyethers, synthetic initiator is 2-butanols, and polymerization single polymerization monomer is oxyethane and epoxy cyclohexane, and the polymerization degree of oxyethane is 40, and the polymerization degree of epoxy cyclohexane is 15, number-average molecular weight is 3304g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1.8:0.8, and the consumption of catalyzer is 2.0% of polyethers quality.Take one-ended hydroxy polyethers 1mol (3304g), 2,2-dimethylated pentanedioic acid acid anhydride 1.8mol, catalyzer ortho phosphorous acid 66.08g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 150 ℃, insulation reaction 6h.Then in reactor, add hexalin 0.8mol, insulation continues reaction 2.5h.In reaction system, add KHCO
3be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:6, and catalyst levels is 2.15% of one-ended hydroxy polyethers quality.Take 2-(chloromethyl) allyl group-trimethyl silane 6mol, catalyzer cetyltriethylammonium bromide 71.04g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 140 ℃, insulation reaction 6h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 94.8%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 95.9%, and two key retention rates are 99.4%.
Embodiment 7
One-ended hydroxy polyethers, synthetic initiator is 1-amylalcohol, polymerization single polymerization monomer is oxyethane, tetrahydrofuran (THF) and epoxy cyclohexane, the polymerization degree of oxyethane is 40, the polymerization degree of tetrahydrofuran (THF) is 15, and the polymerization degree of epoxy cyclohexane is 10, and number-average molecular weight is 3908g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:2:1, and the consumption of catalyzer is 2.3% of polyethers quality.Take one-ended hydroxy polyethers 1mol (3908g), 1,2-cyclohexyl dicarboxylic acid acid anhydride 2mol, catalyzer tosic acid 89.88g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 160 ℃, insulation reaction 7h.Then in reactor, add 1-octanol 1mol, insulation continues reaction 3h.In reaction system, add K
2cO
3be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:7, and catalyst levels is 2.3% of one-ended hydroxy polyethers quality.Take the bromo-1-octene of 8-7mol, catalyzer myristyl trimethylammonium bromide 89.88g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 150 ℃, insulation reaction 8h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 95.4%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 96.9%, and two key retention rates are 99.6%.
Embodiment 8
One-ended hydroxy polyethers, synthetic initiator is 2-amylalcohol, and polymerization single polymerization monomer is oxyethane, propylene oxide and tetrahydrofuran (THF), and the polymerization degree of oxyethane is 40, and the polymerization degree of propylene oxide is 30, and the polymerization degree of tetrahydrofuran (THF) is 20, and number-average molecular weight is 5028g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:2.2:1.2, and the consumption of catalyzer is 2.5% of polyethers quality.Take one-ended hydroxy polyethers 1mol (5028g), 2-phenyl Pyroglutaric acid 2.2mol, catalyst n KC-9130.2g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 170 ℃, insulation reaction 8h.Then in reactor, add 1-stearyl alcohol 1.2mol, insulation continues reaction 3.5h.In reaction system, add MgCO
3be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:8, and catalyst levels is 2.65% of one-ended hydroxy polyethers quality.Take the chloro-1-undecylene of 11-8mol, catalyzer D201 quaternary ammonium resin 133.24g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 120 ℃, insulation reaction 10h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 96.5%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 97.9%, and two key retention rates are 99.5%.
Embodiment 9
One-ended hydroxy polyethers, synthetic initiator is 1-hexanol, polymerization single polymerization monomer is oxyethane, propylene oxide, tetrahydrofuran (THF) and epoxy cyclohexane, the polymerization degree of oxyethane is 30, the polymerization degree of propylene oxide is 20, the polymerization degree of tetrahydrofuran (THF) is 10, and the polymerization degree of epoxy cyclohexane is 10, and number-average molecular weight is 4282g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:2.5:1.5, and the consumption of catalyzer is 2.8% of polyethers quality.Take one-ended hydroxy polyethers 1mol (4282g), 3-nitro-1,8-naphthalic acid acid anhydride 2.5mol, catalyst n KC-9119.9g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 180 ℃, insulation reaction 10h.Then in reactor, add 1-lauryl alcohol 1.5mol, insulation continues reaction 2h.In reaction system, add CaCO
3be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:10, and catalyst levels is 3% of one-ended hydroxy polyethers quality.Take methacrylic bromine 10mol, catalyzer D301R quaternary ammonium resin 128.46g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 110 ℃, insulation reaction 4h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 97.7%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 98.9%, and two key retention rates are 99.6%.
Embodiment 10
One-ended hydroxy polyethers, synthetic initiator is 1-octanol, and polymerization single polymerization monomer is oxyethane, propylene oxide and tetrahydrofuran (THF), and the polymerization degree of oxyethane is 40, and the polymerization degree of propylene oxide is 20, and the polymerization degree of tetrahydrofuran (THF) is 10, and number-average molecular weight is 3770g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:3:2, and the consumption of catalyzer is 5.5% of polyethers quality.Take one-ended hydroxy polyethers 1mol (3770g), pyridine-3,4-dicarboxylic anhydride 3mol, catalyzer tosic acid 207.4g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 100 ℃, insulation reaction 3h.Then in reactor, add isopropylcarbinol 2mol, insulation continues reaction 2h.In reaction system, add Ca (HCO
3)
2be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:2, and catalyst levels is 5% of one-ended hydroxy polyethers quality.Take 4-1-chloro-4-methyl-benzene 2mol, catalyzer Tetrabutyl amonium bromide 188.5g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 130 ℃, insulation reaction 3h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 98.2%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 98.4%, and two key retention rates are 99.2%.
Embodiment 11
One-ended hydroxy polyethers, synthetic initiator is 1-decanol, and polymerization single polymerization monomer is oxyethane, and the polymerization degree of oxyethane is 100, and number-average molecular weight is 4558g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1.2:0.2, and the consumption of catalyzer is 1.5% of polyethers quality.Take one-ended hydroxy polyethers 1mol (4558g), Succinic anhydried 1.2mol, catalyzer vitriol oil 68.37g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 110 ℃, insulation reaction 2h.Then in reactor, add phenylcarbinol 0.2mol, insulation continues reaction 3h.In reaction system, add Al (OH)
3be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:1.25, and catalyst levels is 2.5% of one-ended hydroxy polyethers quality.Take the bromo-1-phenyl-1-of 3-propylene 1.25mol, catalyzer D392 quaternary ammonium resin 113.95g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 120 ℃, insulation reaction 6h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 97.5%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 98.9%, and two key retention rates are 99.7%.
Embodiment 12
One-ended hydroxy polyethers, synthetic initiator is methyl alcohol, and polymerization single polymerization monomer is oxyethane and 2-toluene glycidyl ether, and the polymerization degree of oxyethane is that the polymerization degree of 150,2-toluene glycidyl ether is 18, and number-average molecular weight is 9584g/mol.The mol ratio of one-ended hydroxy polyethers/acid anhydrides/small molecular alcohol is 1:1.5:0.5, and the consumption of catalyzer is 3% of polyethers quality.Take one-ended hydroxy polyethers 1mol (9584g), Pyroglutaric acid 1.5mol, catalyst n KC-9287.52g.Above-mentioned substance is joined in enclosed high pressure reactor, be warmed up to 125 ℃, insulation reaction 3.5h.Then in reactor, add ethanol 0.5mol, insulation continues reaction 2.2h.In reaction system, add NaOH to be neutralized to neutrality.Volatile matter is removed in decompression, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxylate salt.
One-ended hydroxy polyethers/unsaturated halogenating agent mol ratio is 1:3, and catalyst levels is 2.65% of one-ended hydroxy polyethers quality.Take chlorallylene 3mol, catalyzer Cetyltrimethylammonium bromide 253.98g, above-mentioned substance is joined in polyether intermediate reactor, be warming up to 125 ℃, insulation reaction 6h.The unreacted halogenating agent of reclaim under reduced pressure is also removed volatile impunty, removes by filter insoluble substance, obtains the large monomer of pure esterification.The add-on of one-ended hydroxy polyethers of take is measurement standard, and the mass yield of final solid residue is 98.2%, and the esterification yield that goes out the large monomer of esterification by titration measuring is 99.1%, and two key retention rates are 99.5%.
Claims (10)
1. a preparation method for the large monomer of esterification for polycarboxylate water-reducer, is characterized in that: comprise the following steps:
1) the carboxylic acid salinization of the terminal hydroxy group of one-ended hydroxy polyethers reaction: at 100-180 ℃, one-ended hydroxy polyethers reacts under catalyzer existence condition with acid anhydrides, after reaction 1-10h, in reaction system, add small molecular alcohol, insulation continues reaction 1-3h, and the reaction pressure of previous reaction is reaction system self pressure; Rear decompression vacuum pumping is removed volatile matter, removes by filter insoluble substance, obtains the polyether intermediate that end group is carboxyl.Utilize the polyether intermediate that alkaline reagents is carboxyl by above-mentioned end group to neutralize neutrality, the polyether intermediate that formation end group is carboxylate salt;
In described reaction, the mol ratio of one-ended hydroxy polyethers and acid anhydrides is 1:(1-3); The add-on of small molecular alcohol is to compare the molar weight of the acid anhydrides that one-ended hydroxy polyethers adds; The usage quantity of alkaline reagents be take reaction system and is reached PH and be as the criterion as neutrality;
2) esterification of the polyether intermediate that end group is carboxylate salt: at 80-150 ℃, the polyether intermediate that is carboxylate salt by the end group of step (1) gained adds reactor together with unsaturated halogenating agent, under catalyst action, react 1-10h, keep temperature of reaction decompression vacuum pumping to remove volatile matter, remove by filter insoluble substance, obtain the large monomer of pure esterification;
In described esterification, the polyether intermediate that end group is carboxylate salt and the mol ratio of unsaturated halogenating agent are 1:(1.1-10); Catalyzer usage quantity is for initially to add between the 1%-5% of end hydroxy polyether quality;
The large monomer of gained esterification has unsaturated double-bond and following feature structure:
Wherein, R is the alkyl segment in the initiator structure of one-ended hydroxy polyethers described in step (1); R
1and R
2representing the group in unsaturated halogenating agent structure described in step (1), is H atom or alkyl segment.
2. method according to claim 1, is characterized in that: catalysts described in step (1) is homogeneous phase or the heterogeneous catalyst of the vitriol oil, tosic acid, ortho phosphorous acid, strong acidic ion resin NKC-9, Lewis acid, solid acid or heteropolyacid; The usage quantity of catalyzer is the 1%-5% of polyethers quality.
3. method according to claim 1, is characterized in that: described in step (1), one-ended hydroxy polyethers has following structure:
Its number-average molecular weight is between 200-10000;
Described in step (1) in the structure of one-ended hydroxy polyethers:
The monomer corresponding to structural unit of A representative is oxyethane, and what a represented is the polymerization degree of oxirane monomers, and numerical value is between 0-220;
The monomer corresponding to structural unit of B representative is propylene oxide, and what b represented is the polymerization degree of propylene oxide monomer, and numerical value is between 0-170;
The monomer corresponding to structural unit of C representative is tetrahydrofuran (THF), and what c represented is the polymerization degree of tetrahydrofuran monomers, and numerical value is between 0-130;
The monomer corresponding to structural unit of D representative is epoxy cyclohexane, and what d represented is the polymerization degree of epoxy cyclohexane monomer, and numerical value is between 0-100;
The monomer corresponding to structural unit of E representative is glycidyl ether, and monomer whose structural formula is
r wherein
3in group, include one or several in alkyl group, naphthenic hydrocarbon group, phenyl ring group, heterocyclic group, siloxanes group; What e represented is the polymerization degree of Racemic glycidol ether monomer, and numerical value is between 0-20;
The initiator that R is corresponding is the one-ended hydroxy alcohol between carbon atom number 1-20, is selected from any one in straight chain, side chain, naphthenic hydrocarbon, heterocycle or the aromatic series single hydroxyl alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 1-amylalcohol, 2-amylalcohol, hexalin, phenylcarbinol, 1-octanol, isooctyl alcohol, furans-3-methyl alcohol, triethyl silicane alcohol, 1-decanol, 1-undecyl alcohol, 1-stearyl alcohol.
4. method according to claim 3, it is characterized in that: the glycidyl ether corresponding to structural unit of E representative refers to: ethyl ether, isopropyl glycidyl ether, glycidyl isobutyl ether, tertiary butyl glycidyl ether, butylglycidyl ether, octyl glycidyl ether, lauryl diglycidyl ether, tetradecyl glycidyl ether, glycidyl cetyl ether, 2-toluene glycidyl ether, benzyl glycidyl ether, 1, 2-epoxy-3-phenoxypropane, 4-methoxyphenyl glycidyl ether, 4-nonyl benzene glycidyl ether, Racemic glycidol furfuryl ether, 3-glycidyl ether oxygen base propyl trimethoxy silicane, (3-glycidoxy propyl group) dimethylethoxysilane, 3-[(2, 3)-epoxy the third oxygen] propyl group methyl dimethoxysilane, diethoxymethyl [(3-Oxyranyle methoxy) propyl group] silane, any one in 3-glycidyl ether oxygen base propyl-triethoxysilicane.
5. method according to claim 1, is characterized in that: acid anhydrides described in step (1) is not contain the cyclic acid anhydride of polymerisable pair of key or triple bond, be selected from Succinic anhydried, Tetra hydro Phthalic anhydride, biphenyl acid anhydrides, methane amide succinyl oxide, succinyl oxide, methylsuccinic acid acid anhydride, 2, 2-dimethyl succinic anhydride, phenylsuccinic acid acid anhydride, 2, 3-pyridine dicarboxylic acid acid anhydride, pyridine-3, 4-dicarboxylic anhydride, Pyroglutaric acid, 2-phenyl Pyroglutaric acid, 3-methylglutaric acid acid anhydride, 2, 2-dimethylated pentanedioic acid acid anhydride, 3, 3-dimethylated pentanedioic acid acid anhydride, 3, 3-tetramethylene Pyroglutaric acid, 3-(tertiary butyl dimethyl Si base) Pyroglutaric acid, 3-oxaspiro [5, 5] undecane-2, 4-diketone, 1, 2-cyclohexyl dicarboxylic acid acid anhydride, 1, 8-naphthalene dicarboxylic anhydride, 3-nitro-1, 8-naphthalic anhydride, 4-amino-1, 8-naphthalic anhydride, NA-acid anhydrides, N-methyl-isatin acid anhydrides, any one in N-Z-L-aspartic anhydride.
6. method according to claim 1, is characterized in that: described in step (1), small molecular alcohol is single hydroxyl alcohol;
Its carbon atom is between 1-20, and carbon-chain structure comprises one or several in the groups such as straight chain, side chain, naphthenic hydrocarbon, aromatic series, heterocycle;
Described small molecular alcohol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, hexalin, primary isoamyl alcohol, 1-heptanol, isooctyl alcohol, 1-lauryl alcohol, 1-stearyl alcohol, phenylcarbinol, triethyl silicane alcohol, tetrahydrochysene-3-furfuralcohol, furans-3-methyl alcohol etc.
7. method according to claim 1, is characterized in that: described in step (1), alkaline reagents is Na
2cO
3, NaHCO
3, K
2cO
3, KHCO
3, MgCO
3, CaCO
3, Ca (HCO
3)
2liOH, NaOH, KOH, Mg (OH)
2, Al (OH)
3, Ca (OH)
2, one or several the mixture mixing with arbitrary proportion in ammonia, quadrol, propylene diamine, triethylamine.
8. method according to claim 1, is characterized in that: unsaturated halogenating agent described in step (2) is the unsaturated halohydrocarbon containing unsaturated double-bond and haloid element,
In its structure, carbon atom number is between 3-20, comprises one or several in straight chain group, branched group, naphthenic hydrocarbon group, aromatic group, heterocyclic group in carbon-chain structure.
9. method according to claim 8, it is characterized in that: the described unsaturated halogenating agent of step (2) is selected from chlorallylene, 1-chlorine-2-methyl-1-propylene, methallyl chloride, allyl bromide 98, the bromo-2-methyl-1-propylene of 1-, methacrylic bromine, 1,3,2-CMB, bromo-3 methyl-2-butenes of 1-, the chloro-1-butylene of 3-, 3, 3-dimethyl-allyl bromine, allyl iodide, the chloro-1-cyclopentenes of 1-, 2-(chloromethyl) allyl group-trimethyl silane, 2-chloroacrylonitrile, 2-bromopropylene nitrile, methacrylic iodine, the chloro-1-hexene of 6-, the bromo-1-octene of 8-, the bromo-1-decene of 10-, the chloro-1-undecylene of 11-, the bromo-1-undecylene of 11-, cinnamyl chloride, the bromo-1-phenyl-1-of 3-propylene, any one in 4-1-chloro-4-methyl-benzene.
10. method according to claim 1, it is characterized in that: described in step (2), catalyzer is phase-transfer catalyst, be selected from triethylamine, methyl trioctylphosphine brometo de amonio, triethyl methyl brometo de amonio, tributyl-methyl phosphonium brometo de amonio, tetrabutylammonium chloride, Tetrabutyl amonium bromide, etamon chloride, phenyl trimethylammonium bromide, phenyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium Neutral ammonium fluoride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyltriethylammonium bromide, octadecyl trimethyl ammonium chloride, myristyl trimethylammonium bromide, any one in Sodium dodecylbenzene sulfonate.
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| CN110078909A (en) * | 2019-04-28 | 2019-08-02 | 上海元业体育科技有限公司 | A kind of phosphorous silane-terminated polyether and preparation method thereof |
| CN110078909B (en) * | 2019-04-28 | 2021-08-20 | 上海元业体育科技有限公司 | Phosphorus-containing silane terminated polyether and preparation method thereof |
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