CN104193985B - 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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- CN104193985B CN104193985B CN201410456734.0A CN201410456734A CN104193985B CN 104193985 B CN104193985 B CN 104193985B CN 201410456734 A CN201410456734 A CN 201410456734A CN 104193985 B CN104193985 B CN 104193985B
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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 type compound, specifically a kind of polycarboxylate water-reducer esterification polymeric monomer
Preparation method.
Technical background
Polycarboxylate water-reducer be it is a kind of by acrylic compounds, polyether macromonomer and other monomers copolymerization with certain point
The polymer of son amount.Because it has the advantages that high water reducing rate, high-collapse-retentivity, mobility holding capacity be good, low-dosage, in water
Use in a large number in the construction projects such as electricity, highway, nuclear power and high ferro.With building for high-rise building, high residential building, large stadium etc.
If civilian commerical ready-mixed concrete is growing to the demand of polycarboxylate water-reducer.
One of copolyether polymeric monomer that esterification polymeric monomer is commonly used as polycarboxylate water-reducer, in its structure polymerizable is contained
Unsaturated double-bond and with provide it is sterically hindered based on polyether segment.There is material impact to the performance of polycarboxylate water-reducer.
Building-up process to being esterified polymeric monomer is optimized, and esterification polymeric monomer of the synthesis with better quality, is current polycarboxylic acids diminishing
The focus and difficult point of agent area research.
Ma Baoguo etc. (inquire into, Chinese building material science and technology by the synthesizing method of monomer of polycarboxylic type water-reducer
.2007, (2), 50-52) synthetic method of ester type polyethers is concluded and arranged, industrial and academic research field at present
The method of synthesis ester type polyethers is more with direct esterification.
Patent CN 102746507A with direct esterification as synthetic method, with acrylic compounds, poly glycol monomethyl ether as original
Material, under the conditions of 90-130 DEG C, reacts 6-10h, has synthesized the higher esterification polymeric monomer of esterification yield.
Patent CN 102504232A with direct esterification as synthetic method, with itaconic acid, poly glycol monomethyl ether as original
Material, under the conditions of 80-120 DEG C, reacts 4-8h, has synthesized the higher esterification polymeric monomer of esterification yield.
Patent CN 101125743 with direct esterification as synthetic method, with poly glycol monomethyl ether or Polyethylene Glycol,
Acrylic compounds are raw material, under the conditions of 110-140 DEG C, reaction 5h or so, synthesized esterification yield it is higher and can long-time storage not
Rotten esterification polymeric monomer.
Patent CN 101041570 with direct esterification as synthetic method, with acrylic compounds, poly glycol monomethyl ether as original
Material, under the conditions of 95-130 DEG C, reacts 3.5-5.5h, has synthesized the higher esterification polymeric monomer of esterification yield.
(methacrylic acid (poly-) glycol ether monoesters synthesising process research [D], 2009.) with direct esterification such as Lei Haiqin
For research method, the catalyst to poly glycol monomethyl ether and the esterification process of methacrylic acid of system, esterification temperature and ester
The factors such as change time are studied and optimized.The reaction condition of optimization is：Reaction temperature is 122 DEG C, and the response time is 6h, is obtained
The high esterification polymeric monomer of esterification yield is arrived.
The method of direct esterification synthesis esterification polymeric monomer is simple, is affected by changing the reaction such as enzymatic synthesis condition and rate of charge
Factor, can obtain the higher esterification polymeric monomer of esterification yield, be current industrial main method.But this method is not
Foot part is that reaction needs to carry out at a higher temperature, because acrylic compounds are the more active monomers of a class, is easily existed
High temperature is issued is conigenous poly- grade for side reaction, causes partial esterification polymeric monomer not have polymerization activity.
The content of the invention
Used as the higher synthesis polycarboxylate water-reducer direct esterification for being esterified polymeric monomer of esterifying efficiency, it is because reaction
Temperature is higher, causes side reaction more, therefore the esterification polymeric monomer for obtaining has the problems such as not possessing polymerization activity.The present invention is provided
A kind of course of reaction need not use water entrainer, the method for the high synthesis esterification polymeric monomer of esterification yield and double bond retention rate.
Technical scheme：The present invention is to provide a kind of preparation method of polycarboxylate water-reducer with esterification polymeric monomer, including with
Lower step：
1) the carboxylic acid salinization reaction of the terminal hydroxy group of one-ended hydroxy polyethers：At 100-180 DEG C, one-ended hydroxy polyethers and anhydride
React under catalyst existence condition, after reaction 1-10h, add small molecular alcohol, insulation to continue to react 1-3h in reaction system,
The reaction pressure of previous reaction is reaction system pressure itself；Afterwards decompression vacuum pumping removes volatile material, is filtered to remove insoluble
Property material, obtain end group be carboxyl polyether intermediate.Using alkaline reagent by above-mentioned end group in the polyether intermediate of carboxyl
With to neutrality, the polyether intermediate that end group is carboxylate is formed；
One-ended hydroxy polyethers and the mol ratio of anhydride are 1 in the reaction:(1-3)；The addition of small molecular alcohol is to compare
The mole of the anhydride that one-ended hydroxy polyethers is added；The usage amount of alkaline reagent reaches PH and is defined for neutrality by reaction system；
The one-ended hydroxy polyethers in the presence of catalyst, to epoxyalkane ring-opening polymerisation preparation is carried out by initiator,
Preparation method and catalyst are that therefore not to repeat here known to this professional field practitioner.Wherein, initiator is one-ended hydroxy
Alcohol, one-ended hydroxy alcohol prepares one-ended hydroxy polyethers, the alkyl of one-ended hydroxy alcohol to epoxy alkane ring opening polymerization as initiator
Segment is the end alkyl group of one-ended hydroxy polyethers.Polymerization epoxyalkane be oxirane, expoxy propane, tetrahydrofuran,
One or several in 7-oxa-bicyclo[4.1.0 or glycidyl ether.
2) end group is the esterification of the polyether intermediate of carboxylate：At 80-150 DEG C, by the end group obtained by step (1)
Polyether intermediate for carboxylate adds reactor together with unsaturated halogenating agent, and 1-10h is reacted under catalyst action, protects
Hold reaction temperature decompression vacuum pumping and remove volatile material, be filtered to remove insoluble substance, obtain pure esterification polymeric monomer；
In step (2) esterification, end group for polyether intermediate and the unsaturated halogenating agent of carboxylate mole
Than for 1:(1.1-10)；Catalyst usage amount is to be initially added between the 1%-5% of end hydroxy polyether quality.
Gained esterification polymeric monomer 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), R1And R2Ride instead of walk
Suddenly the group described in (1) in unsaturated halogenating agent structure, is H atom or alkyl segment.
Catalysts described in step (1) are concentrated sulphuric acid, p-methyl benzenesulfonic acid, ortho phosphorous acid, strong acidic ion resin
NKC-9, Lewis acid, solid acid, heteropoly acid etc. be homogeneous or heterogeneous catalysis.The usage amount of catalyst is polyether quality
1%-5%.
One-ended hydroxy polyethers has following structure described in step (1)：
Its number-average molecular weight is 200-
Between 10000.
Described in step (1) in the structure of one-ended hydroxy polyethers：
The corresponding initiators of R are the alkyl segment of the one-ended hydroxy alcohol between carbon atom number 1-20, belong to this kind of alcohol
There is methanol, ethanol, 1- propanol, 2- propanol, n-butyl alcohol, 2- butanol, 1- amylalcohols, 2- amylalcohols, Hexalin, benzyl alcohol, 1- capryl alcohol, different
Straight chain, side chain, cycloalkane, the heterocycles such as capryl alcohol, furan -3- methanol, triethyl silicane alcohol, 1-decanol, 1- undecyl alcohols, 1- octadecanol
Or aromatic mono alcohol.From the carbon atom number and the difference of carbon-chain structure of initiator, the list prepared can be adjusted
The hydrophilic and oleophilic performance of end hydroxy polyether, so as to meet the use demand of different application occasion.
It is big single that end moieties R bases in the one-ended hydroxy polyether structure ultimately remain in the esterification of synthesized polycarboxylic acids
In body, this R base is identical with the R bases in esterification polymeric monomer structure with the polycarboxylic acids
The corresponding monomer of construction unit that A is represented is oxirane, the degree of polymerization for oxirane monomers that a is represented, number
Value is between 0-220；
The corresponding monomer of construction unit that B is represented is expoxy propane, the degree of polymerization for propylene oxide monomer that b is represented, number
Value is between 0-170；
The corresponding monomer of construction unit that C is represented is tetrahydrofuran, the degree of polymerization for tetrahydrofuran monomers that c is represented, number
Value is between 0-130；
The corresponding monomer of construction unit that D is represented is 7-oxa-bicyclo[4.1.0, the polymerization for 7-oxa-bicyclo[4.1.0 monomer that d is represented
Degree, numerical value is between 0-100.
The corresponding monomer of construction unit that E is represented is glycidyl ether, and monomer structural formula isIts
Middle R3Include in group one kind in alkyl group, cycloalkane group, benzene radicals, heterocyclic group, siloxane group or
Person is several.What e was represented is the degree of polymerization of glycidyl ether monomers, and numerical value is between 0-20.
Belong to this glycidyl ether has ethyl ether, isopropyl glycidyl ether, glycidyl isobutyl
Base ether, tertiary butyl glycidyl ether, butyl glycidyl ether, octyl glycidyl ether, lauryl diglycidyl ether, the tetradecane
Base glycidyl ether, glycidylhexadecyl ether, 2- toluene glycidyl ethers, benzyl glycidyl ether, 1,2- epoxy -3-
Phenoxypropane, 4- methoxyphenyl glycidyl ethers, 4- nonyl benzene glycidyl ethers, (+)-2,3-Epoxy-1-propanol furfuryl ether, 3- (+)-2,3-Epoxy-1-propanols
Ether epoxide propyl trimethoxy silicane, (3- glycidoxypropyl groups) dimethylethoxysilane, 3- [oxygen of (2,3)-epoxy third]
Hydroxypropyl methyl dimethoxysilane, diethoxymethyl [(3- oxiranylmethoxies) propyl group] silane, 3- glycidyl ether oxygens
Base propyl-triethoxysilicane etc..
The synthetic method of one-ended hydroxy polyethers described in technical scheme, is here known to this professional field practitioner
Do not repeat.
Anhydride is free from the cyclic acid anhydride of polymerisable double bond or three keys described in step (1).
Step (1) anhydride is selected from succinic anhydride, phthalic anhydride, biphenyl anhydride, Methanamide succinic anhydrides, succinum
Anhydride, methyl succinic anhydride, 2,2- dimethyl succinic anhydrides, phenylsuccinic acid acid anhydride, 2,3- dipicolinic acid acid anhydrides, pyridine -3,4-
Dicarboxylic anhydride, glutaric anhydride, 2- phenyl glutaric anhydrides, 3- methylglutaric acid acid anhydrides, 2,2- dimethylated pentanedioic acid acid anhydrides, 3,3- dimethyl
Glutaric anhydride, 3,3- tetramethyleneglutaric acid acid anhydrides, 3- (tertiary butyl dimethyl Si base) glutaric anhydride, 3- oxaspiros [5,5] ten
One alkane -2,4- diketone, 1,2- cyclohexyl dicarboxylic acid acid anhydrides, 1,8- naphthalene dicarboxylic anhydrides, 3- nitro -1,8- naphthalic anhydrides, 4- amino -1,8-
Naphthalic anhydride, NA- anhydride, N-methyl-isatin anhydride, N-Z-L- aspartic anhydrides etc..
Small molecular alcohol described in step (1) is single hydroxyl alcohol.The purpose for adding small molecular alcohol is to react away unnecessary ring-type
Anhydride, generation one end is carboxylate, and the other end is the compound of carboxylic acid.Prevent remaining cyclic acid anhydride from being formed in N-process
Dicarboxylate, forms the esterified material containing double unsaturated double-bonds in follow-up esterification.Because the esterified material containing double unsaturated bonds,
Easily cause and partial cross-linked reaction occur during later stage synthesis polycarboxylate water-reducer, affect the performance of polycarboxylate water-reducer.
The carbon atom of small molecular alcohol described in step (1) between 1-20, carbon-chain structure comprising straight chain, side chain, cycloalkane,
One or several in the groups such as aromatic series, heterocycle.
Step 1) small molecular alcohol be selected from methanol, ethanol, propanol, butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, hexamethylene
Alcohol, isoamyl alcohol, 1-heptanol, isooctanol, 1- lauryl alcohols, 1- octadecanol, benzyl alcohol, triethyl silicane alcohol, tetrahydrochysene -3- furan first
Alcohol, furan -3- methanol etc..
End hydroxy polyether is reacted described in step (1) does not have water to produce with the reaction of cyclic acid anhydride, may be seldom a part of
After esterification open loop, the carboxyl without esterification can continue to be there is esterification and produces anhydride again with polyethers or small molecular alcohol
Unboiled water, but the yield of water is seldom, for esterification itself is without king-sized impact.So in end hydroxy polyether and acid
Can select not using water entrainer in the reaction of acid anhydride, this is a technical advantage in the present invention.
Alkaline reagent described in step (1) is Na2CO3、NaHCO3、K2CO3、KHCO3、MgCO3、CaCO3、Ca(HCO3)2LiOH、NaOH、KOH、Mg(OH)2、Al(OH)3、Ca(OH)2, ammonia, ethylenediamine, propane diamine, the one kind in triethylamine etc. or
Several mixture.
On the one hand the unsaturated halogenated hydrocarbons for adding have the effect for promoting esterification yield to improve more in step (2), also may be used in addition
As reaction dissolvent, to reduce the viscosity of reactant mixture.After the completion of reaction, unreacted unsaturated halogenated hydrocarbons can reduce pressure
Steam and used as esterifying reagent again after collection.
Unsaturated halogenating agent can be described as the unsaturated halogen containing unsaturated double-bond and halogen described in step (2)
For hydrocarbon, in its structure carbon atom number between 3-20, in carbon-chain structure comprising straight chain group, branched group, cycloalkane group,
One or several in the groups such as aromatic group, heterocyclic group.
Unsaturated halogenating agent described in step (2) is selected from allyl chloride, 1- chlorine-2-methyl-1-propylenes, methacrylic
The bromo- 2- methyl-1-propylenes of chlorine, allyl bromide, bromoallylene, 1-, methallyl bromide, 1,3,2-CMB, the bromo- 3 methyl -2- of 1-
The chloro- 1-butylene of butylene, 3-, 3,3- dimethallyl bromides, allyl iodide, the chloro- 1- cyclopentenes of 1-, 2- (chloromethyl) pi-allyl-
Trimethyl silane, 2- chloroacrylonitriles, 2- bromopropene nitriles, methacrylic iodine, the chloro- 1- hexenes of 6-, the bromo- 1- octenes of 8-, 10- are bromo-
The chloro- 1- endecatylenes of 1-decene, 11-, the bromo- 1- endecatylenes of 11-, cinnamyl chloride, the bromo- 1- phenyl -1- propylene of 3-, 4- chloromethyls
Styrene etc..
Catalyst described in step (2) is phase transfer catalyst, selected from having triethylamine, methyl trioctylphosphine ammonium bromide, three second
Ylmethyl ammonium bromide, tributyl-methyl phosphonium ammonium bromide, tetrabutylammonium chloride, tetrabutyl ammonium bromide, tetraethylammonium chloride, phenyl front three
Base ammonium bromide, phenyl trimethicone ammonium chloride, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium fluoride,
Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, cetyltriethylammonium bromide, octadecyl trimethyl
Ammonium chloride, myristyl trimonium ammonium bromide, dodecylbenzene sodium sulfonate etc..
Phase transfer catalyst described in step (2) can also be the immobilized resin for having a quaternary ammonium salt, using quaternary ammonium resin
Advantage is that catalyst is easy to be separated with reaction mass, so as to reach the effect of catalyst recycling.Urge with phase transfer
The quaternary ammonium resin of agent function is including D201, D261, D280, D290, D296, D301R, D301G, D370, D392 etc..
Described in step (2) in esterification, the stability of unsaturated halogenating agent is higher, and end group is the polyethers of carboxylate
Stable chemical nature under intermediate High Temperature High Pressure, it is not required that with polymerization inhibitor, so as to reduce polymerization inhibitor to follow-up polycarboxylic acids
The adverse effect of high performance water-reducer.
The synthesis step of polymeric monomer is esterified in the present invention can be described as：By one-ended hydroxy polyethers, anhydride, catalyst according to
Certain proportion is added in enclosed high pressure reactor, is warmed up to assigned temperature, insulation reaction for a period of time after, add and residual acid
The equimolar small molecular alcohol of acid anhydride amount, continues insulation reaction for a period of time, adds alkaline reagent to be neutralized to neutrality, and decompression vacuum pumping is removed
Volatile material is removed, insoluble substance is filtered to remove, the polyether intermediate that end group is carboxylate is obtained.
A certain amount of unsaturated halogenating agent and catalyst are added in polyether intermediate, design temperature are warming up to and are protected
Temperature reaction a period of time, the complete unsaturated halogenating agent of recovered under reduced pressure unreacted, leftover materials are filtered to remove insoluble substance, obtain
To esterification polymeric monomer.
The method of the invention, it is not necessary to using organic solvent as water entrainer, and reaction condition is gentle, side reaction is few,
The esterification polymeric monomer polymerizable activity of acquisition is high, is that a kind of polycarboxylate water-reducer for preparing of high-efficiency environment friendly is esterified the new of polymeric monomer
Method.
Specific embodiment
The present invention is described in detail below by example, these examples are merely illustrative, do not represent the restriction present invention
The scope of application, medicine used or reagent can be bought by usual channel in embodiment.
Embodiment 1
One-ended hydroxy polyethers, synthesis initiator is methanol, and polymerized monomer is oxirane and (+)-2,3-Epoxy-1-propanol furfuryl ether, epoxy second
The degree of polymerization of alkane is 5, and the degree of polymerization of (+)-2,3-Epoxy-1-propanol furfuryl ether is 2, and number-average molecular weight is 560g/mol.One-ended hydroxy polyethers/anhydride/
The mol ratio of small molecular alcohol is 1：1：0, the consumption of catalyst is the 0% of polyether quality.Weigh one-ended hydroxy polyethers 1mol
(560g), succinic anhydride 1mol, above-mentioned substance is added in enclosed high pressure reactor, is warmed up to 100 DEG C, insulation reaction 1h.
NaOH is added to be neutralized to neutrality in reaction system.Volatile material is removed under reduced pressure, insoluble substance is filtered to remove, end group is obtained
For the polyether intermediate of carboxylate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：1, catalyst amount is one-ended hydroxy polyether quality
1%.Allyl chloride 1mol, catalyst triethyl methyl ammonium bromide 5.60g are weighed, above-mentioned substance polyether intermediate is added to into anti-
In answering kettle, 80 DEG C are warming up to, insulation reaction 1h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatile impurity, crosses and filters
Insoluble substance is removed, pure esterification polymeric monomer is obtained.As measurement criteria, final solid is remained addition with one-ended hydroxy polyethers
The mass yield of excess is 93.4%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is 87.5%, double bond retention rate
For 99.2%.
Embodiment 2
One-ended hydroxy polyethers, synthesis initiator is ethanol, and polymerized monomer is 7-oxa-bicyclo[4.1.0, and the degree of polymerization is 20, and number is divided equally
Son amount is 2006g/mol.The mol ratio of one-ended hydroxy polyethers/anhydride/small molecular alcohol is 1：1.05：0.05, the consumption of catalyst
For the 1% of polyether quality.One-ended hydroxy polyethers 1mol (2006g), phthalic anhydride 1.05mol are weighed, catalyst is to toluene
Sulfonic acid 20.06g.Above-mentioned substance is added in enclosed high pressure reactor, 110 DEG C is warmed up to, insulation reaction 2h.Then to reaction
Methanol 0.05mol, insulation is added to continue to react 1h in kettle.KOH is added to be neutralized to neutrality in reaction system.Volatilization is removed under reduced pressure
Property material, be filtered to remove insoluble substance, obtain end group be carboxylate polyether intermediate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：2, catalyst amount is one-ended hydroxy polyether quality
1.5%.Methallyl chloride 2mol, catalyst methyl trioctylphosphine ammonium bromide 30.09g are weighed, above-mentioned substance is added to into polyethers
In intermediate reaction kettle, 105 DEG C are warming up to, insulation reaction 2.5h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatility
Impurity, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.With the addition of one-ended hydroxy polyethers as metering mark
Standard, the mass yield of final solid residue is 94.2%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is
89.5%, double bond retention rate is 99.4%.
Embodiment 3
One-ended hydroxy polyethers, synthesis initiator is 1- propanol, and polymerized monomer is expoxy propane, and the degree of polymerization is 30, and number is divided equally
Son amount is 1800g/mol.The mol ratio of one-ended hydroxy polyethers/anhydride/small molecular alcohol is 1：1.1：0.1, the consumption of catalyst is
The 1.2% of polyether quality.One-ended hydroxy polyethers 1mol (1800g), Methanamide succinic anhydrides 1.1mol are weighed, catalyst is to toluene
Sulfonic acid 21.6g.Above-mentioned substance is added in enclosed high pressure reactor, 120 DEG C is warmed up to, insulation reaction 2.2h.Then to anti-
Addition 1- propanol 0.1mol in kettle, insulation is answered to continue to react 1.5h.LiOH is added to be neutralized to neutrality in reaction system.Decompression is removed
Volatile material is removed, insoluble substance is filtered to remove, the polyether intermediate that end group is carboxylate is obtained.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：3, catalyst amount is one-ended hydroxy polyether quality
1.75%.The bromo- 2- methyl-1-propylenes 3mol of 1-, catalyst tetrabutylammonium chloride 31.5g are weighed, above-mentioned substance is added to poly-
In ether intermediate reaction kettle, 120 DEG C are warming up to, insulation reaction 3h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatility
Impurity, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.With the addition of one-ended hydroxy polyethers as metering mark
Standard, the mass yield of final solid residue is 94.7%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is
90.2%, double bond retention rate is 99.6%.
Embodiment 4
One-ended hydroxy polyethers, synthesis initiator is 2- propanol, and polymerized monomer is tetrahydrofuran, and the degree of polymerization is 40, and number is divided equally
Son amount is 2940g/mol.The mol ratio of one-ended hydroxy polyethers/anhydride/small molecular alcohol is 1：1.2：0.2, the consumption of catalyst is
The 1.5% of polyether quality.Weigh one-ended hydroxy polyethers 1mol (2940g), methyl succinic anhydride 1.2mol, catalyst concentrated sulphuric acid
44.1g.Above-mentioned substance is added in enclosed high pressure reactor, 130 DEG C is warmed up to, insulation reaction 3.0h.Then to reactor
Middle addition isoamyl alcohol 0.2mol, insulation continues to react 1.8h.Na is added in reaction system2CO3It is neutralized to neutrality.It is removed under reduced pressure
Volatile material, is filtered to remove insoluble substance, obtains the polyether intermediate that end group is carboxylate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：4, catalyst amount is one-ended hydroxy polyether quality
1.9%.1,3,2-CMB 4mol, catalyst phenyl trimethicone ammonium chloride 55.86g are weighed, above-mentioned substance is added
To in polyether intermediate reactor, 125 DEG C are warming up to, insulation reaction 4h.The unreacted halogenating agent of recovered under reduced pressure and removing wave
The property sent out impurity, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.With the addition of one-ended hydroxy polyethers as metering
Standard, the mass yield of final solid residue is 95.2%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is
93.2%, double bond retention rate is 99.7%.
Embodiment 5
One-ended hydroxy polyethers, synthesis initiator is n-butyl alcohol, and polymerized monomer is expoxy propane and tetrahydrofuran, expoxy propane
The degree of polymerization be 20, the degree of polymerization of tetrahydrofuran is 20, and number-average molecular weight is 2674g/mol.One-ended hydroxy polyethers/anhydride/little
The mol ratio of molecule alcohol is 1：1.5：0.5, the consumption of catalyst is the 1.7% of polyether quality.Weigh one-ended hydroxy polyethers 1mol
(2674g), glutaric anhydride 1.5mol, catalyst concentrated sulphuric acid 45.46g.Above-mentioned substance is added in enclosed high pressure reactor, is risen
Temperature to 140 DEG C, insulation reaction 5h.Then tert-butyl alcohol 0.5mol, insulation is added to continue to react 2.0h in reactor.To reactant
NaHCO is added in system3It is neutralized to neutrality.Volatile material is removed under reduced pressure, insoluble substance is filtered to remove, end group is obtained for carboxylic acid
The polyether intermediate of salt.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：5, catalyst amount is one-ended hydroxy polyether quality
2.0%.The chloro- 1-butylene 5mol of 3-, catalyst Dodecyl trimethyl ammonium chloride 53.48g are weighed, above-mentioned substance is added to poly-
In ether intermediate reaction kettle, 130 DEG C are warming up to, insulation reaction 5h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatility
Impurity, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.With the addition of one-ended hydroxy polyethers as metering mark
Standard, the mass yield of final solid residue is 95.7%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is
95.3%, double bond retention rate is 99.5%.
Embodiment 6
One-ended hydroxy polyethers, synthesis initiator is 2- butanol, and polymerized monomer is oxirane and 7-oxa-bicyclo[4.1.0, epoxy second
The degree of polymerization of alkane is 40, and the degree of polymerization of 7-oxa-bicyclo[4.1.0 is 15, and number-average molecular weight is 3304g/mol.One-ended hydroxy polyethers/acid
The mol ratio of acid anhydride/small molecular alcohol is 1：1.8：0.8, the consumption of catalyst is the 2.0% of polyether quality.Weigh one-ended hydroxy polyethers
1mol (3304g), 2,2- dimethylated pentanedioic acid acid anhydride 1.8mol, catalyst ortho phosphorous acid 66.08g.Above-mentioned substance is added to close
In closing autoclave, 150 DEG C are warmed up to, insulation reaction 6h.Then Hexalin 0.8mol, insulation is added to continue in reactor
Reaction 2.5h.KHCO is added in reaction system3It is neutralized to neutrality.Volatile material is removed under reduced pressure, insoluble thing is filtered to remove
Matter, obtains the polyether intermediate that end group is carboxylate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：6, catalyst amount is one-ended hydroxy polyether quality
2.15%.2- (chloromethyl) pi-allyl-trimethyl silane 6mol, catalyst cetyltriethylammonium bromide 71.04g are weighed,
Above-mentioned substance is added in polyether intermediate reactor, 140 DEG C is warming up to, insulation reaction 6h.The unreacted halogen of recovered under reduced pressure
For reagent and volatile impurity is removed, be filtered to remove insoluble substance, obtain pure esterification polymeric monomer.With one-ended hydroxy polyethers
Addition be measurement criteria, the mass yield of final solid residue is 94.8%, goes out esterification by titration measuring big single
The esterification yield of body is 95.9%, and double bond retention rate is 99.4%.
Embodiment 7
One-ended hydroxy polyethers, synthesis initiator is 1- amylalcohols, and polymerized monomer is oxirane, tetrahydrofuran and epoxy hexamethylene
Alkane, the degree of polymerization of oxirane is 40, and the degree of polymerization of tetrahydrofuran is 15, and the degree of polymerization of 7-oxa-bicyclo[4.1.0 is 10, the equal molecule of number
Measure as 3908g/mol.The mol ratio of one-ended hydroxy polyethers/anhydride/small molecular alcohol is 1：2：1, the consumption of catalyst is polyethers matter
The 2.3% of amount.Weigh one-ended hydroxy polyethers 1mol (3908g), 1,2- cyclohexyl dicarboxylic acid acid anhydride 2mol, catalyst p-methyl benzenesulfonic acid
89.88g.Above-mentioned substance is added in enclosed high pressure reactor, 160 DEG C is warmed up to, insulation reaction 7h.Then in reactor
1- capryl alcohol 1mol, insulation is added to continue to react 3h.K is added in reaction system2CO3It is neutralized to neutrality.Volatility thing is removed under reduced pressure
Matter, is filtered to remove insoluble substance, obtains the polyether intermediate that end group is carboxylate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：7, catalyst amount is one-ended hydroxy polyether quality
2.3%.The bromo- 1- octenes 7mol of 8-, catalyst myristyl trimonium ammonium bromide 89.88g are weighed, above-mentioned substance is added to poly-
In ether intermediate reaction kettle, 150 DEG C are warming up to, insulation reaction 8h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatility
Impurity, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.With the addition of one-ended hydroxy polyethers as metering mark
Standard, the mass yield of final solid residue is 95.4%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is
96.9%, double bond retention rate is 99.6%.
Embodiment 8
One-ended hydroxy polyethers, synthesis initiator is 2- amylalcohols, and polymerized monomer is oxirane, expoxy propane and tetrahydrochysene furan
Mutter, the degree of polymerization of oxirane is 40, the degree of polymerization of expoxy propane is 30, the degree of polymerization of tetrahydrofuran is 20, number-average molecular weight
For 5028g/mol.The mol ratio of one-ended hydroxy polyethers/anhydride/small molecular alcohol is 1：2.2：1.2, the consumption of catalyst is polyethers
The 2.5% of quality.Weigh one-ended hydroxy polyethers 1mol (5028g), 2- phenyl glutaric anhydride 2.2mol, catalyst n KC-9
130.2g.Above-mentioned substance is added in enclosed high pressure reactor, 170 DEG C is warmed up to, insulation reaction 8h.Then in reactor
1- octadecanol 1.2mol, insulation is added to continue to react 3.5h.MgCO is added in reaction system3It is neutralized to neutrality.It is removed under reduced pressure
Volatile material, is filtered to remove insoluble substance, obtains the polyether intermediate that end group is carboxylate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：8, catalyst amount is one-ended hydroxy polyether quality
2.65%.The chloro- 1- endecatylenes 8mol of 11-, catalyst D201 quaternary ammonium resin 133.24g are weighed, above-mentioned substance is added to
In polyether intermediate reactor, 120 DEG C are warming up to, insulation reaction 10h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatilization
Property impurity, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.With the addition of one-ended hydroxy polyethers as metering mark
Standard, the mass yield of final solid residue is 96.5%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is
97.9%, double bond retention rate is 99.5%.
Embodiment 9
One-ended hydroxy polyethers, synthesis initiator is 1- hexanols, and polymerized monomer is oxirane, expoxy propane, tetrahydrofuran
And 7-oxa-bicyclo[4.1.0, the degree of polymerization of oxirane is 30, and the degree of polymerization of expoxy propane is 20, and the degree of polymerization of tetrahydrofuran is 10,
The degree of polymerization of 7-oxa-bicyclo[4.1.0 is 10, and number-average molecular weight is 4282g/mol.One-ended hydroxy polyethers/anhydride/small molecular alcohol mole
Than for 1：2.5：1.5, the consumption of catalyst is the 2.8% of polyether quality.Weigh one-ended hydroxy polyethers 1mol (4282g), 3- nitre
Base -1,8- naphthalic anhydride 2.5mol, catalyst n KC-9 119.9g.Above-mentioned substance is added in enclosed high pressure reactor,
180 DEG C are warmed up to, insulation reaction 10h.Then 1- lauryl alcohol 1.5mol, insulation is added to continue to react 2h in reactor.To anti-
Answer and add in system CaCO3It is neutralized to neutrality.Volatile material is removed under reduced pressure, insoluble substance is filtered to remove, obtaining end group is
The polyether intermediate of carboxylate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：10, catalyst amount is one-ended hydroxy polyether quality
3%.Methallyl bromide 10mol, catalyst D301R quaternary ammonium resin 128.46g are weighed, above-mentioned substance is added to into polyethers
In intermediate reaction kettle, 110 DEG C are warming up to, insulation reaction 4h.The unreacted halogenating agent of recovered under reduced pressure and to remove volatility miscellaneous
Matter, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.Addition with one-ended hydroxy polyethers as measurement criteria,
The mass yield of final solid residue is 97.7%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is 98.9%,
Double bond retention rate is 99.6%.
Embodiment 10
One-ended hydroxy polyethers, synthesis initiator is 1- capryl alcohol, and polymerized monomer is oxirane, expoxy propane and tetrahydrochysene furan
Mutter, the degree of polymerization of oxirane is 40, the degree of polymerization of expoxy propane is 20, the degree of polymerization of tetrahydrofuran is 10, number-average molecular weight
For 3770g/mol.The mol ratio of one-ended hydroxy polyethers/anhydride/small molecular alcohol is 1：3：2, the consumption of catalyst is polyether quality
5.5%.Weigh one-ended hydroxy polyethers 1mol (3770g), pyridine -3,4- dicarboxylic anhydride 3mol, catalyst p-methyl benzenesulfonic acid
207.4g.Above-mentioned substance is added in enclosed high pressure reactor, 100 DEG C is warmed up to, insulation reaction 3h.Then in reactor
Isobutanol 2mol, insulation is added to continue to react 2h.Ca (HCO are added in reaction system3)2It is neutralized to neutrality.Volatilization is removed under reduced pressure
Property material, be filtered to remove insoluble substance, obtain end group be carboxylate polyether intermediate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：2, catalyst amount is one-ended hydroxy polyether quality
5%.4- 1-chloro-4-methyl-benzene 2mol, catalyst tetrabutyl ammonium bromide 188.5g are weighed, above-mentioned substance is added in the middle of polyethers
In precursor reactant kettle, 130 DEG C are warming up to, insulation reaction 3h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatile impurity, mistake
Insoluble substance is filtered, pure esterification polymeric monomer is obtained.Addition with one-ended hydroxy polyethers is final solid as measurement criteria
The mass yield of body residue is 98.2%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is 98.4%, and double bond is protected
Rate is stayed to be 99.2%.
Embodiment 11
One-ended hydroxy polyethers, synthesis initiator is 1-decanol, and polymerized monomer is oxirane, and the degree of polymerization of oxirane is
100, number-average molecular weight is 4558g/mol.The mol ratio of one-ended hydroxy polyethers/anhydride/small molecular alcohol is 1：1.2：0.2, catalysis
The consumption of agent is the 1.5% of polyether quality.One-ended hydroxy polyethers 1mol (4558g), succinic anhydride 1.2mol are weighed, catalyst is dense
Sulphuric acid 68.37g.Above-mentioned substance is added in enclosed high pressure reactor, 110 DEG C is warmed up to, insulation reaction 2h.Then to reaction
Benzyl alcohol 0.2mol, insulation is added to continue to react 3h in kettle.Al (OH) is added in reaction system3It is neutralized to neutrality.Decompression is removed
Volatile material is removed, insoluble substance is filtered to remove, the polyether intermediate that end group is carboxylate is obtained.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：1.25, catalyst amount is one-ended hydroxy polyethers matter
The 2.5% of amount.The bromo- 1- phenyl -1- propylene 1.25mol of 3-, catalyst D392 quaternary ammonium resin 113.95g are weighed, by above-mentioned thing
Matter is added in polyether intermediate reactor, is warming up to 120 DEG C, insulation reaction 6h.The unreacted halogenating agent of recovered under reduced pressure is simultaneously
Volatile impurity is removed, insoluble substance is filtered to remove, pure esterification polymeric monomer is obtained.With the addition of one-ended hydroxy polyethers
For measurement criteria, the mass yield of final solid residue is 97.5%, goes out to be esterified the esterification of polymeric monomer by titration measuring
Rate is 98.9%, and double bond retention rate is 99.7%.
Embodiment 12
One-ended hydroxy polyethers, synthesis initiator is methanol, and polymerized monomer is oxirane and 2- toluene glycidyl ethers, ring
The degree of polymerization of oxidative ethane is 18 for the degree of polymerization of 150,2- toluene glycidyl ethers, and number-average molecular weight is 9584g/mol.Single-ended hydroxyl
The mol ratio of base polyethers/anhydride/small molecular alcohol is 1：1.5：0.5, the consumption of catalyst is the 3% of polyether quality.Weigh single-ended
Hydroxy polyethers 1mol (9584g), glutaric anhydride 1.5mol, catalyst n KC-9 287.52g.Above-mentioned substance is added to into closed height
In pressure reactor, 125 DEG C are warmed up to, insulation reaction 3.5h.Then ethanol 0.5mol, insulation is added to continue to react in reactor
2.2h.NaOH is added to be neutralized to neutrality in reaction system.Volatile material is removed under reduced pressure, insoluble substance is filtered to remove, is obtained
To the polyether intermediate that end group is carboxylate.
One-ended hydroxy polyethers/unsaturation halogenating agent mol ratio is 1：3, catalyst amount is one-ended hydroxy polyether quality
2.65%.Allyl chloride 3mol, catalyst Cetyltrimethylammonium bromide 253.98g are weighed, above-mentioned substance is added to poly-
In ether intermediate reaction kettle, 125 DEG C are warming up to, insulation reaction 6h.The unreacted halogenating agent of recovered under reduced pressure simultaneously removes volatility
Impurity, is filtered to remove insoluble substance, obtains pure esterification polymeric monomer.With the addition of one-ended hydroxy polyethers as metering mark
Standard, the mass yield of final solid residue is 98.2%, and the esterification yield for going out to be esterified polymeric monomer by titration measuring is
99.1%, double bond retention rate is 99.5%.
Claims (10)
1. a kind of polycarboxylate water-reducer use is esterified the preparation method of polymeric monomer, it is characterised in that：Comprise the following steps：
1) the carboxylic acid salinization reaction of the terminal hydroxy group of one-ended hydroxy polyethers：At 100-180 DEG C, one-ended hydroxy polyethers is being urged with anhydride
React under agent existence condition, after reaction 1-10h, small molecular alcohol is added in reaction system, insulation continues to react 1-3h, aforementioned
The reaction pressure of reaction is reaction system pressure itself；Afterwards decompression vacuum pumping removes volatile material, is filtered to remove insoluble thing
Matter, obtains the polyether intermediate that end group is carboxyl；Polyether intermediate neutralization using alkaline reagent by above-mentioned end group for carboxyl is arrived
Neutrality, forms the polyether intermediate that end group is carboxylate；
One-ended hydroxy polyethers and the mol ratio of anhydride are 1 in the reaction:(1-3)；The addition of small molecular alcohol is single-ended to compare
The mole of the anhydride that hydroxy polyethers are added；The usage amount of alkaline reagent reaches PH and is defined for neutrality by reaction system；
2) end group is the esterification of the polyether intermediate of carboxylate：It is carboxylic by the end group obtained by step (1) at 80-150 DEG C
The polyether intermediate of hydrochlorate adds reactor together with unsaturated halogenating agent, and 1-10h is reacted under catalyst action, keeps anti-
Answer temperature decompression vacuum pumping to remove volatile material, be filtered to remove insoluble substance, obtain pure esterification polymeric monomer；
In the esterification, end group is 1 for the polyether intermediate and the mol ratio of unsaturated halogenating agent of carboxylate:(1.1-
10)；Catalyst usage amount is to be initially added between the 1%-5% of end hydroxy polyether quality；
Gained esterification polymeric monomer has unsaturated double-bond and following feature structure：
Wherein, R is the alkyl segment described in step (1) in the initiator structure of one-ended hydroxy polyethers；R1And R2Represent step
(2) group described in unsaturated halogenating agent structure, is H atom or alkyl segment.
2. method according to claim 1, it is characterised in that：Catalysts described in step (1) be concentrated sulphuric acid, to first
Benzenesulfonic acid, ortho phosphorous acid, strong acidic ion resin NKC-9, Lewis acid, solid acid or heteropoly acid it is homogeneous or heterogeneous
Catalyst；The usage amount of catalyst is the 1%-5% of polyether quality.
3. method according to claim 1, it is characterised in that：One-ended hydroxy polyethers has following knot described in step (1)
Structure：
Its number-average molecular weight is between 200-10000；
Described in step (1) in the structure of one-ended hydroxy polyethers：
The corresponding monomer of construction unit that A is represented is oxirane, and the degree of polymerization for oxirane monomers that a is represented, numerical value exists
Between 0-220；
The corresponding monomer of construction unit that B is represented is expoxy propane, and the degree of polymerization for propylene oxide monomer that b is represented, numerical value exists
Between 0-170；
The corresponding monomer of construction unit that C is represented is tetrahydrofuran, and the degree of polymerization for tetrahydrofuran monomers that c is represented, numerical value exists
Between 0-130；
The corresponding monomer of construction unit that D is represented is 7-oxa-bicyclo[4.1.0, the degree of polymerization for 7-oxa-bicyclo[4.1.0 monomer that d is represented, number
Value is between 0-100；
The corresponding monomer of construction unit that E is represented is glycidyl ether, and monomer structural formula isWherein R3
Include a kind of or several in alkyl group, cycloalkane group, benzene radicals, heterocyclic group, siloxane group in group
Kind；What e was represented is the degree of polymerization of glycidyl ether monomers, and numerical value is between 0-20；
The corresponding initiators of R are the one-ended hydroxy alcohol between carbon atom number 1-20, selected from methanol, ethanol, 1- propanol, 2- third
Alcohol, n-butyl alcohol, 2- butanol, 1- amylalcohols, 2- amylalcohols, Hexalin, benzyl alcohol, 1- capryl alcohol, isooctanol, furan -3- methanol, triethyl group
Silanol, 1-decanol, 1- undecyl alcohols, 1- octadecanol.
4. method according to claim 3, it is characterised in that：The corresponding glycidyl ether of construction unit that E is represented is referred to：
Ethyl ether, isopropyl glycidyl ether, glycidyl isobutyl ether, tertiary butyl glycidyl ether, butyl shrink
Glycerin ether, octyl glycidyl ether, lauryl diglycidyl ether, myristyl glycidyl ether, glycidylhexadecyl
Base ether, 2- toluene glycidyl ethers, benzyl glycidyl ether, 1,2- epoxy -3- phenoxypropanes, 4- methoxyphenyls shrink sweet
Oily ether, 4- nonyl benzene glycidyl ethers, (+)-2,3-Epoxy-1-propanol furfuryl ether, 3- glycydoxy trimethoxy silanes, (3- epoxies
Propoxypropyl) dimethylethoxysilane, 3- [oxygen of (2,3)-epoxy third] hydroxypropyl methyl dimethoxysilane, diethoxy first
Any one in base [(3- oxiranylmethoxies) propyl group] silane, 3- glycydoxy triethoxysilanes.
5. method according to claim 1, it is characterised in that：Anhydride is free from polymerisable double bond described in step (1)
Or three key cyclic acid anhydride；Selected from succinic anhydride, phthalic anhydride, biphenyl anhydride, Methanamide succinic anhydrides, methyl succinic
Anhydride, 2,2- dimethyl succinic anhydrides, phenylsuccinic acid acid anhydride, 2,3- dipicolinic acid acid anhydrides, pyridine -3,4- dicarboxylic anhydrides, penta 2
Anhydride, 2- phenyl glutaric anhydrides, 3- methylglutaric acid acid anhydrides, 2,2- dimethylated pentanedioic acid acid anhydrides, 3,3- dimethylated pentanedioic acid acid anhydrides, 3,3-
Tetramethyleneglutaric acid acid anhydride, 3- (tertiary butyl dimethyl Si base) glutaric anhydride, 3- oxaspiros [5,5] hendecane -2,4- diketone,
1,2- cyclohexyl dicarboxylic acid acid anhydrides, 1,8- naphthalene dicarboxylic anhydrides, 3- nitro -1,8- naphthalic anhydrides, 4- amino -1,8- naphthalic anhydrides, NA-
Any one in anhydride, N-methyl-isatin anhydride, N-Z-L- aspartic anhydrides.
6. method according to claim 1, it is characterised in that：Small molecular alcohol described in step (1) is single hydroxyl alcohol；
Its carbon atom between 1-20, carbon-chain structure comprising the one kind in straight chain, side chain, cycloalkane, aromatic series, heterocyclic group or
Person is several；
The small molecular alcohol is selected from methanol, ethanol, propanol, butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, Hexalin, isoamyl alcohol, 1-
Enanthol, isooctanol, 1- lauryl alcohols, 1- octadecanol, benzyl alcohol, triethyl silicane alcohol, tetrahydrochysene -3- furancarbinols, furan -3- first
Alcohol.
7. method according to claim 1, it is characterised in that：Alkaline reagent described in step (1) is Na2CO3、NaHCO3、
K2CO3、KHCO3、MgCO3、CaCO3、Ca(HCO3)2LiOH、NaOH、KOH、Mg(OH)2、Al(OH)3、Ca(OH)2, ammonia, second two
One or several the mixture mixed with arbitrary proportion in amine, propane diamine, triethylamine.
8. method according to claim 1, it is characterised in that：Unsaturated halogenating agent is containing insatiable hunger described in step (2)
With double bond and the unsaturated halogenated hydrocarbons of halogen,
Carbon atom number is between 3-20 in its structure, in carbon-chain structure comprising straight chain group, branched group, cycloalkane group,
One or several in aromatic group, heterocyclic group.
9. method according to claim 8, it is characterised in that：Unsaturated halogenating agent described in step (2) is selected from allyl
The bromo- 2- methyl-1-propylenes of base chlorine, 1- chlorine-2-methyl-1-propylenes, methallyl chloride, allyl bromide, bromoallylene, 1-, methacrylic
Bromo- 3 methyl-2-butene of bromine, 1,3,2-CMB, 1-, the chloro- 1-butylene of 3-, 3,3- dimethallyl bromides, pi-allyl
The chloro- 1- cyclopentenes of iodine, 1-, 2- (chloromethyl) pi-allyl-trimethyl silane, 2- chloroacrylonitriles, 2- bromopropene nitriles, methacrylic
The chloro- 1- hexenes of iodine, 6-, the bromo- 1- octenes of 8-, the bromo- 1-decene of 10-, the chloro- 1- endecatylenes of 11-, the bromo- 1- endecatylenes of 11-, meat
Any one in the bromo- 1- phenyl -1- propylene of osmanthus base chlorine, 3-, 4- 1-chloro-4-methyl-benzenes.
10. method according to claim 1, it is characterised in that：Catalyst described in step (2) is phase transfer catalyst,
Selected from have triethylamine, methyl trioctylphosphine ammonium bromide, triethyl methyl ammonium bromide, tributyl-methyl phosphonium ammonium bromide, tetrabutylammonium chloride,
Tetrabutyl ammonium bromide, tetraethylammonium chloride, phenyltrimethylammonium bromide, phenyl trimethicone ammonium chloride, benzyltriethylammoinium chloride,
Benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium fluoride, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride,
Cetyltriethylammonium bromide, octadecyl trimethyl ammonium chloride, myristyl trimonium ammonium bromide, DBSA
Any one in sodium.
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| CN104628930B (en) * | 2015-02-15 | 2016-08-24 | 北京工业大学 | Fatty acid vinyl ester monomer copolymerization is synthesized the method for cement dispersants |
| CN104710580B (en) * | 2015-03-31 | 2017-08-08 | 陕西友邦新材料科技有限公司 | Polycarboxylate superplasticizer mother liquor and preparation method thereof |
| CN104761176B (en) * | 2015-03-31 | 2017-11-10 | 陕西友邦新材料科技有限公司 | Compound polycarboxylate water-reducer and preparation method thereof |
| CN104987472B (en) * | 2015-07-28 | 2017-11-17 | 中建商品混凝土有限公司 | A kind of water reducer for strengthening cement concrete and protecting characteristic of collapsing |
| CN106916292B (en) * | 2015-12-25 | 2019-04-16 | 江苏奥克化学有限公司 | A kind of polyoxyalkyl ether and preparation method thereof, by its resulting polycarboxylate water-reducer and preparation method |
| CN107382129B (en) * | 2017-08-14 | 2020-04-24 | 联泓(江苏)新材料研究院有限公司 | Polycarboxylate superplasticizer, preparation method thereof and cement admixture |
| CN107400188B (en) * | 2017-08-14 | 2019-09-10 | 联泓(江苏)新材料研究院有限公司 | A kind of unsaturated polyether monomer and preparation method thereof, using and polymer obtained |
| CN109721720B (en) * | 2017-10-27 | 2021-05-28 | 辽宁奥克化学股份有限公司 | Ester polyether, preparation method thereof, application of ester polyether in preparation of water reducing agent and water reducing agent prepared from ester polyether |
| CN108948283B (en) * | 2018-05-31 | 2020-10-30 | 台州中知英健机械自动化有限公司 | Phthalic anhydride modified polycarboxylate superplasticizer and preparation method thereof |
| CN109400822B (en) * | 2018-11-09 | 2021-07-20 | 安徽海螺新材料科技有限公司 | Preparation method of slump-retaining polycarboxylate superplasticizer mother liquor |
| CN111348858B (en) * | 2018-12-29 | 2022-03-18 | 江苏苏博特新材料股份有限公司 | Early-strength polycarboxylate superplasticizer and preparation method thereof |
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Address after: No.6 shuiyougang, Gulou District, Nanjing City, Jiangsu Province 210013 Patentee after: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee after: JIANGSU BOTE NEW MATERIALS Co.,Ltd. Address before: 211103, No. 59 West Wan An Road, Jiangning District, Jiangsu, Nanjing Patentee before: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee before: JIANGSU BOTE NEW MATERIALS Co.,Ltd. |