CN103183822B - A kind of unsaturated ammonia ester polyoxyalkyl ether and preparation method thereof - Google Patents
A kind of unsaturated ammonia ester polyoxyalkyl ether and preparation method thereof Download PDFInfo
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Abstract
A kind of unsaturated ammonia ester polyoxyalkyl ether for polycarboxylate water-reducer and preparation method thereof is disclosed.This unsaturated ammonia ester polyoxyalkyl ether has such as formula the structure shown in (1), and in formula, the definition of each symbol is as shown in specification sheets.This unsaturated ammonia ester polyoxyalkyl ether is under certain temperature and pressure and stopper existence, is prepared by alkoxyl group polyoxyalkyl ether and unsaturated isocyanate reaction.Unsaturated ammonia ester polyoxyalkyl ether stability of the present invention is high, has again the terminal double link of high reaction activity simultaneously, therefore can be used for preparing comb shaped polymer and polycarboxylate water-reducer.
Description
Technical field
The present invention relates to a kind of unsaturated ammonia ester polyoxyalkyl ether and preparation method thereof, more specifically, the present invention relates to unsaturated ammonia ester polyoxyalkyl ether of a kind of preparation for polycarboxylate water-reducer and comb-shaped polymer and preparation method thereof.
Background technology
Concrete, as current indispensable material of construction, has stepped into commercialization, high performance epoch.Concrete commercialization, high performance rely on concrete admixture to realize, and wherein the kind of most critical is water reducer, accounts for more than 80% of the total consumption of admixture.There is the poly carboxylic acid series water reducer of combed molecular structure because having the excellent properties such as volume is low, water-reducing rate is high, slump retention is good, become the indispensable component of preparation high performance concrete, and degree of freedom is large on molecular structure, synthetic method is various, high-performance potentiality are large, therefore become the emphasis of recent domestic research and development.
Polycarboxylate water-reducer is a kind of important polymer comb-shaped polymer, normally synthesizes in copolymerization mode under initiator effect with unsaturated polyoxyalkyl ether polymeric monomer and unsaturated carboxylic acid small molecule monomer.The thiazolinyl of large minor comonomer forms vinyl backbone by copolymerization mode, the polyoxy alkyl segment of polyoxyalkyl ether polymeric monomer then forms comb-type structure side chain, wherein unsaturated polyoxyalkyl ether polymeric monomer almost account for that polycarboxylate water-reducer does agent total mass 80%, visible, unsaturated polyoxyalkyl ether polymeric monomer is the vital basic material of water reducer industry.
Disclose a kind of method preparing polycarboxylate water-reducer in CN101531747A, adopt vinylformic acid and methoxy polyoxyethylene ether to carry out esterification and obtain unsaturated carboxylate type Soxylat A 25-7, for the preparation of polycarboxylate water-reducer.But the shortcoming of this unsaturated carboxylate type Soxylat A 25-7 polymeric monomer is: preparation process needs dehydrating step, complex process, esterification is incomplete, has more by product to generate simultaneously, causes unstable product quality; Poor storage stability.
Biopolymer, 10 volumes, 29-95 (2003), disclosing with alkenyl alcohol is that initiator and reacting ethylene oxide are prepared and held the unsaturated Soxylat A 25-7 macromonomer of thiazolinyl, i.e. thiazolinyl ether type polyoxyalkyl ether polymeric monomer.This kind of thiazolinyl ether type polymeric monomer is connected by ehter bond, therefore stable chemical nature, simultaneously without esterification process, simplifies synthesis technique.But the polymerization activity of thiazolinyl ether type polymeric monomer is low, is difficult to realize homogeneous polymerization, causes the side chain distribution of comb-shaped polymer uneven, thus affect its application performance.
Summary of the invention
In order to solve the problem, the invention provides a kind of unsaturated ammonia ester polyoxyalkyl ether, there is the double bond of high reaction activity, utilize urethano to roll into a ball simultaneously and connect Soxylat A 25-7 chain, substantially increase storage and the stability in use of unsaturated ammonia ester polyoxyalkyl ether.When adopting unsaturated ammonia ester polyoxyalkyl ether to prepare comb-shaped polymer, it can be good at and the unsaturated minor comonomer copolyreaction such as vinylformic acid, methacrylic acid, maleic anhydride, vinylbenzene and methylpropene sodium sulfonate, can the degree of closing of modulation polyoxyalkyl ether side chain very well, reach and well disperse application performance.
In addition the present invention also provides a kind of method preparing described unsaturated ammonia ester polyoxyalkyl ether, and this preparation method's step is simple, and double bond retention rate is high, and product ammonia degree of esterification is high, can control its molecular structure and molecular weight well.
On the one hand, the invention provides a kind of unsaturated ammonia ester polyoxyalkyl ether, its structural formula is as shown in formula (1) below:
In formula,
A is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-,
B is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-,
R
1represent H or CH
3,
R
2represent C
1-10alkylidene group, C
6-10arylene or C
2-10containing the alkylidene group of ester group,
R
3represent C
1-10alkyl,
X is expressed as the integer of 0-100,
Y is expressed as the integer of 0-100, and
10≤x+y≤150。
On the other hand, A, B in above-mentioned unsaturated ammonia ester polyoxyalkyl ether are-CH
2cH
2o-, x are the integer of 5-100, and y is the integer of 5-100, are called unsaturated ammonia ester Soxylat A 25-7.
On the other hand, A, B in above-mentioned unsaturated ammonia ester polyoxyalkyl ether are-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-, x are the integer of 5-100, and y is the integer of 5-100, are called unsaturated ammonia ester polyethenoxy ether.
On the other hand, the A in above-mentioned unsaturated ammonia ester polyoxyalkyl ether is-CH
2cH
2o-, B are-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-, x are the integer of 5-100, and y is the integer of 5-100, are called unsaturated ammonia ester EP type polyoxy alkyl block polyethers.
Again on the one hand, the A in above-mentioned unsaturated ammonia ester polyoxyalkyl ether is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-, B are-CH
2cH
2o-, x are the integer of 5-100, and y is the integer of 5-100, are called unsaturated ammonia ester PE type polyoxy alkyl block polyethers.
Again on the one hand, A and B in above-mentioned unsaturated ammonia ester polyoxyalkyl ether is-CH
2cH
2o-or-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-, x are the integer of 5-100, and y is the integer of 5-100, are called unsaturated ammonia ester polyoxy alkyl and mix embedding polyethers.
Again on the one hand, above-mentioned unsaturated ammonia ester polyoxyalkyl ether of the present invention has the weight-average molecular weight of 500 ~ 8000.
In addition, the present invention also provides a kind of method preparing above-mentioned unsaturated ammonia ester polyoxyalkyl ether, and the method comprises the steps:
A, the alkoxyl group polyoxyalkyl ether shown in formula (2) is below heated to 60 ~ 140 DEG C, then adds the stopper of gross weight 0.01 ~ 1%, and stir,
HO(A)
x(B)
yR
3(2)
In formula,
A is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-,
B is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-,
R
3represent C
1-10alkyl,
X is expressed as the integer of 0-100,
Y is expressed as the integer of 0-100, and
10≤x+y≤150；
B, drip in the reaction system deriving from step a below the unsaturated isocyanate shown in formula (3), time for adding 0.5 ~ 4 hour, and to control temperature of reaction be 60 ~ 140 DEG C, reaction pressure is 0.1 ~ 1MPa,
In formula,
R
1represent H or CH
3, and
R
2represent C
1-10alkylidene group, C
6-10arylene or C
2-10containing the alkylidene group of ester group; And
After c, dropping terminate, reaction system is continued reaction 1 ~ 3 hour under the temperature of reaction of 60 ~ 140 DEG C, then removes low boiling component, and be cooled to room temperature, obtain described unsaturated ammonia ester polyoxyalkyl ether.Prepare the reaction mechanism of unsaturated ammonia ester polyoxyalkyl ether as shown in reaction formula (4):
On the one hand, in method of the present invention, described unsaturated isocyanate be selected from following in one or more: vinyl isocyanate, isocyanic acid propylene, 3-pseudoallyl-α, α-dimethylbenzyl isocyanic ester, and isocyanatoethyl, preferred vinyl isocyanate and/or isocyanic acid propylene.
On the other hand, in the method for the invention, described alkoxyl group polyoxyalkyl ether be selected from following in one or more: methoxy polyoxyethylene ether, methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyethers, methoxyl group PE type polyoxy alkyl block polyethers, methoxyl group polyoxy alkyl mixes embedding polyethers, oxyethyl group Soxylat A 25-7, oxyethyl group polyethenoxy ether, oxyethyl group EP type polyoxy alkyl block polyethers, oxyethyl group PE type polyoxy alkyl block polyethers, oxyethyl group polyoxy alkyl mixes embedding polyethers, isopropoxy Soxylat A 25-7, butoxy Soxylat A 25-7, the last of the ten Heavenly stems oxygen base Soxylat A 25-7, the last of the ten Heavenly stems oxygen base polyethenoxy ether, preferred methoxy polyoxyethylene ether, methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyethers, methoxyl group PE type polyoxy alkyl block polyethers, and methoxyl group polyoxy alkyl mixes embedding polyethers.
Again on the one hand, in the method for the invention, described stopper for being selected from para benzoquinone, toluhydroquinone, thiodiphenylamine, MEHQ, one or more in the stoppers such as aromatic nitro compound.
Again on the one hand, in the method for the invention, the mol ratio of described unsaturated isocyanate and described alkoxyl group polyoxyalkyl ether is 1 ~ 1.1: 1.
As used herein, it is disubstituted that term " arylene " refers to that phenyl ring contains, and term " unsaturated ammonia ester EP type polyoxy alkyl block polyethers " refers to that unsaturated urethano group is first connected the compound be then connected with polyethenoxy ether segment with Soxylat A 25-7 segment; Term " unsaturated ammonia ester PE type polyoxy alkyl block polyethers " refers to that unsaturated urethano group is first connected the compound be then connected with Soxylat A 25-7 segment with polyethenoxy ether segment; Term " unsaturated ammonia ester polyoxy alkyl mixes embedding polyethers " refers to the compound of unsaturated urethano group and oxygen Vinyl Ether segment and oxypropylene ether segment lack of alignment.
Compared with end thiazolinyl Soxylat A 25-7 of the prior art, the unsaturated ammonia ester polyoxyalkyl ether stability prepared by the present invention is high, has the terminal double link of high reaction activity simultaneously, can be used for preparing comb shaped polymer and polycarboxylate water-reducer.
In order to understand the present invention better, hereinafter, with reference to embodiment below, the present invention is further illustrated.Unless made separate stipulations herein, the same meaning that scientific and technical terminology used herein is all understood usually with general technical staff of the technical field of the invention.Wherein mentioned material, method and embodiment are below only for illustration of, instead of the restriction to scope of the present invention.
Accompanying drawing explanation
Fig. 1 is unsaturated ammonia ester Soxylat A 25-7 NMR spectrogram.
Embodiment
Enumerate embodiment below and further illustrate the present invention, but the present invention is not by their restriction.
In one embodiment, the invention provides a kind of unsaturated ammonia ester polyoxyalkyl ether, this unsaturated polyether reacts obtained by alkoxyl group polyoxyalkyl ether and unsaturated isocyanate, and weight-average molecular weight is 500 ~ 8000; Wherein, the structural formula of alkoxyl group polyoxy alkyl is such as formula shown in (5):
HO(A)
x(B)
yR
3(5)
In formula (5), A is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-, B are-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-, R
3represent C
1-10alkyl, wherein x is expressed as the integer of 0-100, and y is expressed as the integer of 0-100, and 10≤x+y≤150;
The structural formula of unsaturated isocyanate is such as formula shown in (6):
In formula (6), R
1represent H or CH3, R
2represent C
1-10alkylidene group, C
6-10arylene or C
2-10containing the alkylidene group of ester group.
In one embodiment, described alkoxyl group polyoxyalkyl ether is methoxy polyoxyethylene ether, methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyethers, methoxyl group PE type polyoxy alkyl block polyethers, methoxyl group polyoxy alkyl mixes embedding polyethers, oxyethyl group Soxylat A 25-7, oxyethyl group polyethenoxy ether, oxyethyl group EP type polyoxy alkyl block polyethers, oxyethyl group PE type polyoxy alkyl block polyethers, oxyethyl group polyoxy alkyl mixes embedding polyethers, isopropoxy Soxylat A 25-7, butoxy Soxylat A 25-7, the last of the ten Heavenly stems oxygen base Soxylat A 25-7, the last of the ten Heavenly stems oxygen base polyethenoxy ether, preferred methoxy polyoxyethylene ether, methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyethers, methoxyl group PE type polyoxy alkyl block polyethers, methoxyl group polyoxy alkyl mixes embedding polyethers.When unsaturated ammonia ester polyoxyalkyl ether wherein containing Soxylat A 25-7 chain is for the preparation of polycarboxylate water-reducer, there is higher water-reducing rate and function of slump protection; When the unsaturated ammonia ester polyoxyalkyl ether mixing embedding polyether chain and polyethenoxy ether chain containing polyoxy alkyl block polyether chain, polyoxy alkyl is for the preparation of polycarboxylate water-reducer, there is good water-reducing rate there is low bubble performance simultaneously, can be used for preparing the concrete with property.Above-mentioned alkoxyl group polyoxyalkyl ether can be buied from the market.Such as, methoxy polyoxyethylene ether can be buied from Liaoning AoKe Chemical Co., Ltd with MPEG1000 trade name.
In one embodiment, described unsaturated isocyanate is vinyl isocyanate, isocyanic acid propylene, 3-pseudoallyl-alpha, alpha-dimethylbenzyl isocyanic ester, and the one in isocyanatoethyl, preferred vinyl isocyanate, isocyanic acid propylene.Above-mentioned monomer C is commercially available.Such as, vinyl isocyanate can be buied from sigma-aldrich company.
In one embodiment, unsaturated ammonia ester polyoxyalkyl ether preferred molecular weight is 500 ~ 8000.When unsaturated ammonia ester polyoxyalkyl ether molecular weight lower than 500 time, the polycarboxylate water-reducer side chain of preparation is too short, and dispersing property is poor, and water-reducing rate is low; When the molecular weight of unsaturated ammonia ester polyoxyalkyl ether is greater than 8000, the polycarboxylate water-reducer side chain of preparation is long, causes side chain to be mutually wound around, and dispersing property reduces, and water-reducing rate reduces.
In another embodiment, the invention provides a kind of method preparing unsaturated ammonia ester polyoxyalkyl ether, the method comprises the steps:
A, the alkoxyl group polyoxyalkyl ether shown in formula (7) is below heated to 60 ~ 140 DEG C, then adds the stopper of gross weight 0.01 ~ 1%, and stir,
HO(A)
x(B)
yR
3(7)
In formula,
A is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-,
B is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-or-CH
2cH
2o-,
R
3represent C
1-10alkyl,
X is expressed as the integer of 0-100,
Y is expressed as the integer of 0-100, and
10≤x+y≤150；
B, drip in the reaction system deriving from step a below the unsaturated isocyanate shown in formula (8), time for adding 0.5 ~ 4 hour, and to control temperature of reaction be 60 ~ 140 DEG C, reaction pressure is 0.1 ~ 1MPa,
In formula,
R
1represent H or CH
3, and
R
2represent C
1-10alkylidene group, C
6-10arylene or C
2-10containing the alkylidene group of ester group; And
After c, dropping terminate, reaction system is continued reaction 1 ~ 3 hour under the temperature of reaction of 60 ~ 140 DEG C, then removes low boiling component, and be cooled to room temperature, obtain described unsaturated ammonia ester polyoxyalkyl ether.
In one embodiment, be para benzoquinone for stopper of the present invention, toluhydroquinone, thiodiphenylamine, MEHQ, trinitrobenzene, 1,1-phenylbenzene-2-trinitrophenyl-hydrazine, one or more in 2,2,6,6-tetramethyl piperidine oxide compound.Above-mentioned stopper is conventional initiator well known in the art, can buy by market.
In one embodiment, the mol ratio for unsaturated isocyanate of the present invention and alkoxyl group polyoxyalkyl ether is 1 ~ 1.1: 1.
In embodiments of the invention, temperature is too low, and alkoxyl group polyoxyalkyl ether is in solid-state, is difficult to react with unsaturated isocyanate, and temperature is too high, easily side reaction occurs.Therefore, preferable reaction temperature is 60 ~ 140 DEG C.
Consider that order of addition(of ingredients) and feed rate are on the impact of the unsaturated ammonia ester polyoxyalkyl ether of preparation, in embodiments of the invention, preferably join alkoxyl group polyoxyalkyl ether by unsaturated isocyanate, and preferably in 0.5 ~ 4 hour, complete dropping.When rate of addition is too fast, material reaction is too fierce, and temperature of reaction should not control, and when rate of addition is crossed slow, then affects production efficiency.
In embodiments of the invention, after being preferably added dropwise to complete, reactant is continued reaction 1 ~ 3 hour at the temperature of 60 ~ 140 DEG C, to carry out with reacting fully, be conducive to the utilization ratio improving raw material like this.
In embodiments of the invention, in order to ensure alkoxyl group polyoxyalkyl ether complete reaction, unsaturated isocyanate is slightly excessive, and therefore, reaction terminates rear removed under reduced pressure unsaturated isocyanate, obtains described unsaturated ammonia ester polyoxyalkyl ether.
The synthetic operation of unsaturated ammonia ester polyoxyalkyl ether all carries out under drying nitrogen environment.Various reactant after drying and dehydrating for the synthesis of reaction.
Preparation embodiment 1
Take 400.00g methoxy polyoxyethylene ether (structural formula as shown in Equation 9), join in reaction flask be warming up to 60 DEG C start stirring after add 0.43g thiodiphenylamine and stir, then instill 30.29g vinyl isocyanate, react at 60 DEG C, 0.2MPa carries out, time for adding 1 hour.Under temperature of reaction 60 DEG C of conditions, continue reaction 2 hours after dripping off, then at 60 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis (30 DEG C is that standard substance convert molecular weight with polyoxyethylene glycol), number-average molecular weight is 512g/mol, and weight-average molecular weight is 532g/mol.Measure the DAWNHELEOSII type using Wyatt company to produce, the gel chromatographic columns of the OHpakSB-802.5HQ model using Shodex company to produce.In the following embodiments, when measuring at 30 DEG C, be all carry out under these conditions.
As shown in Equation 10, NMR spectrogram is shown in accompanying drawing 1 to NMR spectrometry unsaturated ammonia ester Soxylat A 25-7 structural formula.The INOVA400M type that Varian company produces is used during mensuration.
Preparation embodiment 2
Take 400.00g oxyethyl group PE type polyoxy alkyl block polyethers (structural formula as shown in Equation 11), join in reaction flask be warming up to 130 DEG C start stirring after add 0.61g benzoquinones and stir, then 5.09g vinyl isocyanate is instilled, reaction is at 130 DEG C, 0.8MPa carries out, time for adding 0.6 hour.Under temperature of reaction 130 DEG C of conditions, continue reaction 2.5 hours after dripping off, then at 130 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis, number-average molecular weight is 5442g/mol, and weight-average molecular weight is 5503g/mol.
NMR spectrometry unsaturated ammonia ester PE type polyoxy alkyl block polyether structure formula as shown in Equation 12.
Preparation embodiment 3
Take 400.00g methoxyl group polyoxy alkyl and mix embedding polyethers (structural formula as shown in Equation 13), join in reaction flask be warming up to 100 DEG C start stirring after add 0.33g toluhydroquinone and stir, then 10.69g isocyanic acid propylene is instilled, reaction is at 100 DEG C, 0.2MPa carries out, time for adding 2 hours.Under temperature of reaction 100 DEG C of conditions, continue reaction 1.5 hours after dripping off, then at 100 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis, number-average molecular weight is 3209g/mol, and weight-average molecular weight is 3250g/mol.
NMR spectrometry unsaturated ammonia ester polyoxy alkyl mixes embedding polyether structure formula as shown in Equation 14.
Preparation embodiment 4
Take 400.00g isopropoxy polyethenoxy ether (structural formula as shown in Equation 15), join in reaction flask be warming up to 80 DEG C start stirring after add 0.82g MEHQ and stir, then 12.41g isocyanic acid propylene is instilled, reaction is at 80 DEG C, 0.2MPa carries out, time for adding 1 hour.Under temperature of reaction 80 DEG C of conditions, continue reaction 3 hours after dripping off, then at 80 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis, number-average molecular weight is 2742g/mol, and weight-average molecular weight is 2776g/mol.
NMR spectrometry unsaturated ammonia ester polyethenoxy ether structural formula as shown in Equation 16.
Preparation embodiment 5
Take 400.00g methoxyl group EP type polyoxy alkyl block polyethers (structural formula as shown in Equation 17), join in reaction flask be warming up to 120 DEG C start stirring after add 0.44g benzoquinones and stir, then 38.15g3-pseudoallyl-α is instilled, α-dimethylbenzyl isocyanic ester, reaction is at 120 DEG C, 0.4MPa carries out, time for adding 1 hour.Under temperature of reaction 120 DEG C of conditions, continue reaction 1.5 hours after dripping off, then at 120 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis, number-average molecular weight is 2327g/mol, and weight-average molecular weight is 2341g/mol.
NMR spectrometry unsaturated ammonia ester EP type polyoxy alkyl block polyether structure formula as shown in Equation 18.
Preparation embodiment 6
Take 400.00g butoxy polyoxy alkyl and mix embedding polyethers (structural formula as shown in Equation 19), join in reaction flask be warming up to 70 DEG C start stirring after add 1.05g benzoquinones and stir, then 23.48g isocyanatoethyl is instilled, reaction is at 100 DEG C, 0.1MPa carries out, time for adding 3 hours.Under temperature of reaction 100 DEG C of conditions, continue reaction 2.5 hours after dripping off, then at 100 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis, number-average molecular weight is 2673g/mol, and weight-average molecular weight is 2691g/mol.
NMR spectrometry unsaturated ammonia ester polyoxy alkyl mixes embedding polyether structure formula as shown in Equation 20.
Preparation embodiment 7
Take 400.00g oxygen in last of the ten Heavenly stems base Soxylat A 25-7 (structural formula as shown in Equation 21), join in reaction flask be warming up to 90 DEG C start stirring after add 0.61g benzoquinones and stir, then instill 11.73g vinyl isocyanate, react at 90 DEG C, 0.3MPa carries out, time for adding 4 hours.Under temperature of reaction 90 DEG C of conditions, continue reaction 2 hours after dripping off, then at 90 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis, number-average molecular weight is 2401g/mol, and weight-average molecular weight is 2430g/mol.
NMR spectrometry unsaturated ammonia ester Soxylat A 25-7 structural formula as shown in Equation 22.
Preparation embodiment 8
Take 400.00g methoxyl group PE type polyoxy alkyl block polyethers (structural formula as shown in Equation 23), join in reaction flask be warming up to 140 DEG C start stirring after add 0.61g benzoquinones and stir, then 4.45g isocyanic acid propylene is instilled, reaction is at 140 DEG C, 0.4MPa carries out, time for adding 1.5 hours.Under temperature of reaction 140 DEG C of conditions, continue reaction 3 hours after dripping off, then at 140 DEG C, vacuum tightness removes low boiling component 1 hour under-0.08MPa condition, is then cooled to room temperature and obtains product.Finally, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis, number-average molecular weight is 7580g/mol, and weight-average molecular weight is 7620g/mol.
NMR spectrometry unsaturated ammonia ester PE type polyoxy alkyl block polyether structure formula as shown in Equation 24.
Application Example 1
Prepare polycarboxylate water-reducer to prepare unsaturated ammonia ester Soxylat A 25-7 obtained in embodiment 1, and consider its application performance.Concrete steps are as follows:
Water at the bottom of 210g, 77g polymeric monomer, 18g vinylformic acid, 7.9g maleic anhydride, 1.9g thiohydracrylic acid is added in the round-bottomed flask of 500ml, separately join ammonium persulfate solution and drip (2.5g ammonium persulphate, 30g water), time for adding is 3 hours, temperature of reaction is 80 ± 2 DEG C, reaction times is 2 hours, aging 1 hour of insulation after reaction.Be cooled to less than 50 DEG C after insulation terminates, being neutralized to pH with sodium hydroxide is 6.0 ~ 7.0, obtains the polycarboxylic acid series high efficiency water reducing agent that solid content is 30%.Detect by JG/T223-2007 " high performance water reducing agent of polyocarboxy acid ", record water-reducing rate more than 27%.
Application Example 2
Prepare polycarboxylate water-reducer to prepare unsaturated ammonia ester EP type polyoxy alkyl block polyethers obtained in embodiment 5, and consider its application performance.Concrete steps are as follows:
Water at the bottom of 170g, 85g polymeric monomer, 10g vinylformic acid, 5.9g acrylamide, 1.9g thiohydracrylic acid is added in the round-bottomed flask of 500ml, separately join ammonium persulfate solution and drip (2.0g ammonium persulphate, 25g water), time for adding is 3 hours, temperature of reaction is 80 ± 2 DEG C, reaction times is 2 hours, aging 1 hour of insulation after reaction.Be cooled to less than 50 DEG C after insulation terminates, being neutralized to pH with sodium hydroxide is 6.0 ~ 7.0, obtains the polycarboxylic acid series high efficiency water reducing agent that solid content is 35%.Detect by JG/T223-2007 " high performance water reducing agent of polyocarboxy acid ", record water-reducing rate more than 29%.
Although described typical embodiment for illustrative purposes, aforementioned explanation should not be construed the restriction to broad scope hereof.Therefore, in the spirit and scope not departing from this paper, those skilled in the art can carry out various different improvement, amendment and replacement.
Claims (9)
1. a unsaturated ammonia ester polyoxyalkyl ether, its structural formula is as shown in formula (1) below:
In formula,
A, B represent any one situation following: A and B is-CH
2cH
2o-; A and B is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-; A is-CH
2cH
2o-, B are-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-; Or A is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-, B are-CH
2cH
2o-;
R
1represent H or CH
3,
R
2represent C
1-10alkylidene group, C
6-10arylene or C
2-10containing the alkylidene group of ester group,
R
3represent C
1-10alkyl,
X is expressed as the integer of 5-100,
Y is expressed as the integer of 5-100, and
10≤x+y≤150；
The weight-average molecular weight of this unsaturated ammonia ester polyoxyalkyl ether is 500 ~ 8000.
2. prepare a method for unsaturated ammonia ester polyoxyalkyl ether according to claim 1, the method comprises the following steps:
A, the alkoxyl group polyoxyalkyl ether shown in formula (2) is below heated to 60 ~ 140 DEG C, then adds the stopper of gross weight 0.01 ~ 1%, and stir,
HO(A)
x(B)
yR
3(2)
In formula,
A, B represent any one situation following: A and B is-CH
2cH
2o-; A and B is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-; A is-CH
2cH
2o-, B are-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-; Or A is-CH
2cH (CH
3) O-or-CH (CH
3) CH
2o-, B are-CH
2cH
2o-;
R
3represent C
1-10alkyl,
X is expressed as the integer of 5-100,
Y is expressed as the integer of 5-100, and
10≤x+y≤150；
B, drip in the reaction system deriving from step a below the unsaturated isocyanate shown in formula (3) or drip vinyl isocyanate, time for adding 0.5 ~ 4 hour, and to control temperature of reaction be 60 ~ 140 DEG C, and reaction pressure is 0.1 ~ 1MPa,
In formula,
R
1represent H or CH
3, and
R
2represent C
1-10alkylidene group, C
6-10arylene or C
2-10containing the alkylidene group of ester group; And
After c, dropping terminate, reaction system is continued reaction 1 ~ 3 hour under the temperature of reaction of 60 ~ 140 DEG C, then removes low boiling component, and be cooled to room temperature, obtain described unsaturated ammonia ester polyoxyalkyl ether.
3. method according to claim 2, wherein said stopper for being selected from para benzoquinone, toluhydroquinone, thiodiphenylamine, MEHQ, trinitrobenzene, 1,1-phenylbenzene-2-trinitrophenyl-hydrazine, one or more in 2,2,6,6-tetramethyl piperidine oxide compound.
4. method according to claim 2, the mol ratio of wherein said unsaturated isocyanate and described alkoxyl group polyoxyalkyl ether is 1 ~ 1.1:1.
5. the method for claim 2, the alkoxyl group polyoxyalkyl ether of wherein said formula (2) be selected from following in one or more: methoxy polyoxyethylene ether, methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyethers, methoxyl group PE type polyoxy alkyl block polyethers, methoxyl group polyoxy alkyl mixes embedding polyethers, oxyethyl group Soxylat A 25-7, oxyethyl group polyethenoxy ether, oxyethyl group EP type polyoxy alkyl block polyethers, oxyethyl group PE type polyoxy alkyl block polyethers, oxyethyl group polyoxy alkyl mixes embedding polyethers, isopropoxy Soxylat A 25-7, butoxy Soxylat A 25-7, the last of the ten Heavenly stems oxygen base Soxylat A 25-7, and the last of the ten Heavenly stems oxygen base polyethenoxy ether.
6. the method for claim 2, the unsaturated isocyanate of wherein said formula (3) be selected from following in one or more: isocyanic acid propylene, 3-pseudoallyl-alpha, alpha-dimethylbenzyl isocyanic ester, and isocyanatoethyl.
7. the method for claim 5, wherein said alkoxyl group polyoxyalkyl ether be selected from following in one or more: methoxy polyoxyethylene ether, methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyethers, methoxyl group PE type polyoxy alkyl block polyethers, and methoxyl group polyoxy alkyl mixes embedding polyethers.
8. the method for claim 6, wherein said unsaturated isocyanate is isocyanic acid propylene.
9. the application of unsaturated ammonia ester polyoxyalkyl ether according to claim 1 in the preparation of polycarboxylate water-reducer and polymer comb-shaped polymer.
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| CN104262612B (en) * | 2014-09-09 | 2018-01-02 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the ester type polyethers containing unsaturated double-bond |
| CN104945633A (en) * | 2015-06-02 | 2015-09-30 | 江苏奥莱特新材料有限公司 | Preparation method of novel polycarboxylic acid type water-reducer |
| TWI541291B (en) * | 2015-06-18 | 2016-07-11 | 明基材料股份有限公司 | Material for contact lenses, method for manufacturing contact lenses and contact lenses obtained thereby |
| CN105778079B (en) * | 2016-03-23 | 2018-06-05 | 联泓新材料有限公司 | A kind of unsaturated polyether monomer and its preparation method and application |
| CN105778013B (en) * | 2016-03-23 | 2018-10-02 | 联泓(江苏)新材料研究院有限公司 | Polycarboxylate water-reducer and preparation method thereof and cement admixture |
| CN107973931A (en) * | 2017-05-19 | 2018-05-01 | 武汉奥克化学有限公司 | A kind of compound stabilizer for polycarboxylic acid water reducer macromer |
| CN111471172B (en) * | 2019-01-24 | 2023-04-14 | 江苏苏博特新材料股份有限公司 | Methyl aromatic ring polyether intermediate, preparation method thereof and application thereof in synthesizing small molecule concrete additive |
| CN114316782B (en) * | 2020-09-30 | 2023-03-31 | 上海飞凯材料科技股份有限公司 | Ultraviolet curing coating, coating product and preparation method |
| CN114316249B (en) * | 2020-09-30 | 2023-08-22 | 上海飞凯材料科技股份有限公司 | Alkylphenol polyoxyethylene (methyl) acrylate, treatment method thereof and coating |
| CN112625232B (en) * | 2020-11-26 | 2023-05-05 | 山西佳维新材料股份有限公司 | Unsaturated amino polyoxyethylene ether and polycarboxylate water reducer, and synthetic method and application thereof |
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