CN103183822A - Unsaturated urethane polyoxyalkyl ether and preparation method thereof - Google Patents
Unsaturated urethane polyoxyalkyl ether and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an unsaturated urethane polyoxyalkyl ether used for a polycarboxylate superplasticizer and a preparation method thereof. The unsaturated urethane polyoxyalkyl ether has a structure as represented by formula (1), and the formula (1) and symbols in the formula (1) are defined in the specification. The unsaturated urethane polyoxyalkyl ether is prepared through reaction of alkoxy polyoxyalkyl ether with unsaturated isocyanate at a certain temperature and a certain pressure in the presence of a polymerization inhibitor. According to the invention, the unsaturated urethane polyoxyalkyl ether has high stability and terminal double bonds with high reaction activity, so the unsaturated urethane polyoxyalkyl ether is applicable to preparation of a comb-shaped polymer and the polycarboxylate superplasticizer.
Description
Technical field
The present invention relates to a kind of unsaturated ammonia ester polyoxy alkyl oxide and preparation method thereof, more specifically, the present invention relates to unsaturated ammonia ester polyoxy alkyl oxide of a kind of preparation for polycarboxylate water-reducer and comb-shaped polymer and preparation method thereof.
Background technology
Concrete has stepped into commercialization, high performance epoch as current indispensable material of construction.Concrete commercialization, high performance rely on concrete admixture to realize that wherein the kind of most critical is water reducer, account for more than 80% of the total consumption of admixture.Poly carboxylic acid series water reducer excellent properties such as volume is low, water-reducing rate is high because having, slump maintenance is good with comb type molecular structure, become the indispensable component of preparation high performance concrete, and degree of freedom is big on molecular structure, synthetic method is various, the high-performance potentiality are big, therefore become in recent years the emphasis of research and development both at home and abroad.
Polycarboxylate water-reducer is a kind of important polymer comb-shaped polymer, normally synthesizes in the copolymerization mode under the initiator effect with the big monomer of unsaturated polyester oxyalkyl ether and unsaturated carboxylic acid small molecule monomer.The thiazolinyl of big minor comonomer forms vinyl backbone by the copolymerization mode, the polyoxy alkyl segment of the big monomer of polyoxy alkyl oxide then constitutes the comb-type structure side chain, wherein the big monomer of unsaturated polyester oxyalkyl ether almost accounts for polycarboxylate water-reducer and does 80% of agent total mass, as seen, the big monomer of unsaturated polyester oxyalkyl ether is the vital basic material of water reducer industry.
Disclose a kind of method for preparing polycarboxylate water-reducer among the CN101531747A, adopted vinylformic acid and methoxy polyoxyethylene ether to carry out esterification and obtain the unsaturated carboxylate type Soxylat A 25-7, for the preparation of polycarboxylate water-reducer.But the shortcoming of the big monomer of this unsaturated carboxylate type Soxylat A 25-7 is: preparation process needs dehydrating step, complex process, and 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 the alkenyl alcohol is the unsaturated polyoxy Vinyl Ether of initiator and reacting ethylene oxide preparation end thiazolinyl macromonomer, the i.e. big monomer of alkene ether type polyoxy alkyl oxide.The big monomer of this class alkene ether type connects by ehter bond, so chemical property is stable, has not had esterification process simultaneously, has simplified synthesis technique.But the polymerization activity of the big monomer of alkene ether type is low, is difficult to realize even polymerization, causes the side chain distribution inequality of comb-shaped polymer, thereby influences its application performance.
Summary of the invention
In order to address the above problem, the invention provides a kind of unsaturated ammonia ester polyoxy alkyl oxide, have two keys of high reaction activity, utilize urethano group to connect the Soxylat A 25-7 chain simultaneously, improved storage and the stability in use of unsaturated ammonia ester polyoxy alkyl oxide greatly.When adopting unsaturated ammonia ester polyoxy alkyl oxide to prepare comb-shaped polymer, it can be good at and unsaturated minor comonomer copolyreaction such as vinylformic acid, methacrylic acid, maleic anhydride, vinylbenzene and methylpropene sodium sulfonate, degree of closing that can fine modulation polyoxy alkyl oxide side chain reaches good dispersion application performance.
The present invention also provides a kind of method for preparing described unsaturated ammonia ester polyoxy alkyl oxide in addition, and this preparation method's step is simple, two key retention rate height, and product ammonia degree of esterification height can be controlled its molecular structure and molecular weight well.
On the one hand, the invention provides a kind of unsaturated ammonia ester polyoxy alkyl oxide, its structural formula is shown in following formula (1):
In the 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
1Expression H or CH
3,
R
2Expression C
1-10Alkylidene group, C
6-10Arylene or C
2-10The alkylidene group that contains ester group,
R
3Expression 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, the B in the above-mentioned unsaturated ammonia ester polyoxy alkyl oxide is-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, the B in the above-mentioned unsaturated ammonia ester polyoxy alkyl oxide is-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 the above-mentioned unsaturated ammonia ester polyoxy alkyl oxide is-CH
2CH
2O-, B is-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 polyether.
On the one hand, the A in the above-mentioned unsaturated ammonia ester polyoxy alkyl oxide is-CH again
2CH (CH
3) O-or-CH (CH
3) CH
2O-, B is-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 polyether.
On the one hand, A and B in the above-mentioned unsaturated ammonia ester polyoxy alkyl oxide are-CH again
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 the embedding polyethers.
On the one hand, above-mentioned unsaturated ammonia ester polyoxy alkyl oxide of the present invention has 500～8000 weight-average molecular weight again.
In addition, the present invention also provides a kind of method for preparing above-mentioned unsaturated ammonia ester polyoxy alkyl oxide, and this method comprises the steps:
A, the alkoxyl group polyoxy alkyl oxide shown in the following formula (2) is heated to 60～140 ℃, adds the stopper of gross weight 0.01～1% then, and stir,
HO(A)
x(B)
yR
3 (2)
In the 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
3Expression 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, in the reaction system that derives from step a, drip below the unsaturated isocyanate shown in the formula (3), 0.5～4 hour dropping time, and to control temperature of reaction be 60～140 ℃, reaction pressure is 0.1～1MPa,
In the formula,
R
1Expression H or CH
3, and
R
2Expression C
1-10Alkylidene group, C
6-10Arylene or C
2-10The alkylidene group that contains ester group; And
After c, dropping finish, reaction system is continued reaction 1～3 hour under 60～140 ℃ temperature of reaction, remove low boiling component then, and be cooled to room temperature, obtain described unsaturated ammonia ester polyoxy alkyl oxide.Prepare the reaction mechanism of unsaturated ammonia ester polyoxy alkyl oxide shown in reaction formula (4):
On the one hand, in method of the present invention, described unsaturated isocyanate is to be selected from following one or more: the isocyanic acid vinyl acetate, isocyanic acid propylene ester, 3-pseudoallyl-α, α-Er Jiajibianji isocyanic ester, and methacrylic acid isocyano-ethyl ester, preferred isocyanic acid vinyl acetate and/or isocyanic acid propylene ester.
On the other hand, in the method for the invention, described alkoxyl group polyoxy alkyl oxide is to be selected from following one or more: methoxy polyoxyethylene ether, the methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyether, methoxyl group PE type polyoxy alkyl block polyether, methoxyl group polyoxy alkyl mixes the embedding polyethers, the oxyethyl group Soxylat A 25-7, the oxyethyl group polyethenoxy ether, oxyethyl group EP type polyoxy alkyl block polyether, oxyethyl group PE type polyoxy alkyl block polyether, oxyethyl group polyoxy alkyl mixes the embedding polyethers, the isopropoxy Soxylat A 25-7, the 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 polyether, methoxyl group PE type polyoxy alkyl block polyether, and methoxyl group polyoxy alkyl mixes the embedding polyethers.
On the one hand, in the method for the invention, described stopper is 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 polyoxy alkyl oxide is 1～1.1: 1 again.
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 polyether " refers to the first compound that is connected with the polyethenoxy ether segment then that is connected with the Soxylat A 25-7 segment of unsaturated urethano group; Term " unsaturated ammonia ester PE type polyoxy alkyl block polyether " refers to the first compound that is connected with the Soxylat A 25-7 segment then that is connected with the polyethenoxy ether segment of unsaturated urethano group; Term " unsaturated ammonia ester polyoxy alkyl mixes the embedding polyethers " refers to the compound of unsaturated urethano group and oxygen Vinyl Ether segment and oxypropylene ether segment lack of alignment.
Compare with end thiazolinyl Soxylat A 25-7 of the prior art, the prepared unsaturated ammonia ester polyoxy alkyl oxide stability of 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, the embodiment with reference to the back is described more specifically the present invention.Unless this paper makes separate stipulations, the employed scientific and technical terminology of this paper all with the same meaning of general technical staff of the technical field of the invention institute common sense.Wherein the embodiment of mentioned material, method and back only is used for explanation, rather than to the restriction of scope of the present invention.
Description of drawings
Fig. 1 is unsaturated ammonia ester Soxylat A 25-7 NMR spectrogram.
Embodiment
Enumerate embodiment below and be described more specifically the present invention, but the present invention is not subjected to their restriction.
In one embodiment, the invention provides a kind of unsaturated ammonia ester polyoxy alkyl oxide, this unsaturated polyether is made by alkoxyl group polyoxy alkyl oxide and unsaturated isocyanate reaction, and weight-average molecular weight is 500～8000; Wherein, the structural formula of alkoxyl group polyoxy alkyl is as the formula (5):
HO(A)
x(B)
yR
3 (5)
In the formula (5), 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
3Expression 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 as the formula (6):
In the formula (6), R
1Expression H or CH3, R
2Expression C
1-10Alkylidene group, C
6-10Arylene or C
2-10The alkylidene group that contains ester group.
In one embodiment, described alkoxyl group polyoxy alkyl oxide is methoxy polyoxyethylene ether, the methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyether, methoxyl group PE type polyoxy alkyl block polyether, methoxyl group polyoxy alkyl mixes embedding polyethers, oxyethyl group Soxylat A 25-7, oxyethyl group polyethenoxy ether, oxyethyl group EP type polyoxy alkyl block polyether, oxyethyl group PE type polyoxy alkyl block polyether, oxyethyl group polyoxy alkyl mixes embedding polyethers, isopropoxy Soxylat A 25-7, the 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, the methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyether, methoxyl group PE type polyoxy alkyl block polyether, methoxyl group polyoxy alkyl mixes the embedding polyethers.The unsaturated ammonia ester polyoxy alkyl oxide that wherein contains the Soxylat A 25-7 chain has higher water-reducing rate and function of slump protection during for the preparation of polycarboxylate water-reducer; When containing unsaturated ammonia ester polyoxy alkyl oxide that polyoxy alkyl block polyether chain, polyoxy alkyl mix embedding polyether chain and polyethenoxy ether chain for the preparation of polycarboxylate water-reducer, have preferably water-reducing rate and have low bubble performance simultaneously, can be used for preparing the concrete with property.Above-mentioned alkoxyl group polyoxy alkyl oxide can be buied from the market.For example, methoxy polyoxyethylene ether can be buied with the MPEG1000 trade name from Liaoning AoKe Chemical Co., Ltd.
In one embodiment, described unsaturated isocyanate is the isocyanic acid vinyl acetate, isocyanic acid propylene ester, 3-pseudoallyl-α, the α-Er Jiajibianji isocyanic ester, and methacrylic acid isocyano-ethyl ester in a kind of, preferred isocyanic acid vinyl acetate, isocyanic acid propylene ester.Above-mentioned monomer C is commercially available.For example, the isocyanic acid vinyl acetate can be buied from sigma-aldrich company.
In one embodiment, unsaturated ammonia ester polyoxy alkyl oxide preferred molecular weight is 500～8000.When the molecular weight of unsaturated ammonia ester polyoxy alkyl oxide was lower than 500, the polycarboxylate water-reducer side chain of preparation was too short, and dispersing property is poor, and water-reducing rate is low; When the molecular weight of unsaturated ammonia ester polyoxy alkyl oxide greater than 8000 the time, the polycarboxylate water-reducer side chain of preparation is long, causes side chain to twine mutually, dispersing property reduces, water-reducing rate reduces.
In another embodiment, the invention provides a kind of method for preparing unsaturated ammonia ester polyoxy alkyl oxide, this method comprises the steps:
A, the alkoxyl group polyoxy alkyl oxide shown in the following formula (7) is heated to 60～140 ℃, adds the stopper of gross weight 0.01～1% then, and stir,
HO(A)
x(B)
yR
3 (7)
In the 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
3Expression 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, in the reaction system that derives from step a, drip below the unsaturated isocyanate shown in the formula (8), 0.5～4 hour dropping time, and to control temperature of reaction be 60～140 ℃, reaction pressure is 0.1～1MPa,
In the formula,
R
1Expression H or CH
3, and
R
2Expression C
1-10Alkylidene group, C
6-10Arylene or C
2-10The alkylidene group that contains ester group; And
After c, dropping finish, reaction system is continued reaction 1～3 hour under 60～140 ℃ temperature of reaction, remove low boiling component then, and be cooled to room temperature, obtain described unsaturated ammonia ester polyoxy alkyl oxide.
In one embodiment, being used for stopper of the present invention is para benzoquinone, toluhydroquinone, thiodiphenylamine, MEHQ, trinitrobenzene, 1,1-phenylbenzene-2-trinitrophenyl-hydrazine, one or more in 2,2,6, the 6-tetramethyl piperidine oxide compound.Above-mentioned stopper is initiator commonly used well known in the art, can be by buying on the market.
In one embodiment, the mol ratio for unsaturated isocyanate of the present invention and alkoxyl group polyoxy alkyl oxide is 1～1.1: 1.
In embodiments of the invention, temperature is low excessively, and alkoxyl group polyoxy alkyl oxide is in solid-state, is difficult to and the unsaturated isocyanate reaction, and temperature is too high, and side reaction takes place easily.Therefore, preferable reaction temperature is 60～140 ℃.
Consider that order of addition(of ingredients) and feed rate to preparing the influence of unsaturated ammonia ester polyoxy alkyl oxide, in embodiments of the invention, preferably join unsaturated isocyanate alkoxyl group polyoxy alkyl oxide, and preferably finished dropping in 0.5～4 hour.When rate of addition was too fast, material reaction was too fierce, and temperature of reaction should not be controlled, and rate of addition is crossed when slow, then influences production efficiency.
In embodiments of the invention, after preferably being added dropwise to complete, reactant is continued reaction 1～3 hour under 60～140 ℃ temperature, to carry out, be conducive to improve utilization ratio of raw materials like this with reacting fully.
In embodiments of the invention, in order to guarantee alkoxyl group polyoxy alkyl oxide complete reaction, unsaturated isocyanate is excessive slightly, and therefore, reaction finishes the back decompression and removes unsaturated isocyanate, obtains described unsaturated ammonia ester polyoxy alkyl oxide.
The synthetic operation of unsaturated ammonia ester polyoxy alkyl oxide all carries out under the drying nitrogen environment.Various reactants through behind the drying and dehydratings for the synthesis of reaction.
Preparation embodiment 1
Take by weighing 400.00g methoxy polyoxyethylene ether (structural formula as shown in Equation 9), join and be warming up to 60 ℃ in the reaction flask and start and stir the back and add the 0.43g thiodiphenylamine and stir, then splash into 30.29g isocyanic acid vinyl acetate, be reflected at 60 ℃, 0.2MPa carry out 1 hour dropping time.Drip off the back and continue reaction 2 hours under 60 ℃ of conditions of temperature of reaction, then at 60 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, by NMR spectrum and GPC determination and analysis product.
According to gpc analysis (30 ℃ is standard substance conversion molecular weight with the polyoxyethylene glycol), number-average molecular weight is 512g/mol, and weight-average molecular weight is 532g/mol.Measure the DAWN HELEOS II type that uses Wyatt company to produce, use the gel chromatographic columns of the OHpak SB-802.5HQ model of Shodex company production.In the following embodiments, when measuring down for 30 ℃, all be under this condition, to carry out.
The unsaturated ammonia ester of NMR spectrometry Soxylat A 25-7 structural formula as shown in Equation 10, the NMR spectrogram is seen accompanying drawing 1.The INOVA 400M type that uses Varian company to produce during mensuration.
Preparation embodiment 2
Take by weighing 400.00g oxyethyl group PE type polyoxy alkyl block polyether (structural formula as shown in Equation 11), join and be warming up to 130 ℃ in the reaction flask and start and stir the back and add the 0.61g benzoquinones and stir, then splash into 5.09g isocyanic acid vinyl acetate, be reflected at 130 ℃, 0.8MPa carry out 0.6 hour dropping time.Drip off the back and continue reaction 2.5 hours under 130 ℃ of conditions of temperature of reaction, then at 130 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, 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.
The unsaturated ammonia ester of NMR spectrometry PE type polyoxy alkyl block polyether structural formula as shown in Equation 12.
Take by weighing 400.00g methoxyl group polyoxy alkyl and mix embedding polyethers (structural formula as shown in Equation 13), join and be warming up to 100 ℃ in the reaction flask and start and stir the back and add the 0.33g toluhydroquinone and stir, then splash into 10.69g isocyanic acid propylene ester, be reflected at 100 ℃, 0.2MPa carry out 2 hours dropping time.Drip off the back and continue reaction 1.5 hours under 100 ℃ of conditions of temperature of reaction, then at 100 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, 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.
The unsaturated ammonia ester of NMR spectrometry polyoxy alkyl mixes embedding polyether structure formula as shown in Equation 14.
Preparation embodiment 4
Take by weighing 400.00g isopropoxy polyethenoxy ether (structural formula as shown in Equation 15), join and be warming up to 80 ℃ in the reaction flask and start and stir the back and add the 0.82g MEHQ and stir, then splash into 12.41g isocyanic acid propylene ester, be reflected at 80 ℃, 0.2MPa carry out 1 hour dropping time.Drip off the back and continue reaction 3 hours under 80 ℃ of conditions of temperature of reaction, then at 80 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, 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.
The unsaturated ammonia ester of NMR spectrometry polyethenoxy ether structural formula as shown in Equation 16.
Take by weighing 400.00g methoxyl group EP type polyoxy alkyl block polyether (structural formula as shown in Equation 17), join and be warming up to 120 ℃ in the reaction flask and start and stir the back and add the 0.44g benzoquinones and stir, then splash into 38.15g 3-pseudoallyl-α, the α-Er Jiajibianji isocyanic ester, be reflected at 120 ℃, 0.4MPa carry out 1 hour dropping time.Drip off the back and continue reaction 1.5 hours under 120 ℃ of conditions of temperature of reaction, then at 120 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, 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.
The unsaturated ammonia ester of NMR spectrometry EP type polyoxy alkyl block polyether structural formula as shown in Equation 18.
Preparation embodiment 6
Take by weighing 400.00g butoxy polyoxy alkyl and mix embedding polyethers (structural formula as shown in Equation 19), join and be warming up to 70 ℃ in the reaction flask and start and stir the back and add the 1.05g benzoquinones and stir, then splash into 23.48g methacrylic acid isocyano-ethyl ester, be reflected at 100 ℃, 0.1MPa carry out 3 hours dropping time.Drip off the back and continue reaction 2.5 hours under 100 ℃ of conditions of temperature of reaction, then at 100 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, 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.
The unsaturated ammonia ester of NMR spectrometry polyoxy alkyl mixes embedding polyether structure formula as shown in Equation 20.
Preparation embodiment 7
Take by weighing 400.00g oxygen in last of the ten Heavenly stems base Soxylat A 25-7 (structural formula as shown in Equation 21), join and be warming up to 90 ℃ in the reaction flask and start and stir the back and add the 0.61g benzoquinones and stir, then splash into 11.73g isocyanic acid vinyl acetate, be reflected at 90 ℃, 0.3MPa carry out 4 hours dropping time.Drip off the back and continue reaction 2 hours under 90 ℃ of conditions of temperature of reaction, then at 90 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, 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.
The unsaturated ammonia ester of NMR spectrometry Soxylat A 25-7 structural formula as shown in Equation 22.
Preparation embodiment 8
Take by weighing 400.00g methoxyl group PE type polyoxy alkyl block polyether (structural formula as shown in Equation 23), join and be warming up to 140 ℃ in the reaction flask and start and stir the back and add the 0.61g benzoquinones and stir, then splash into 4.45g isocyanic acid propylene ester, be reflected at 140 ℃, 0.4MPa carry out 1.5 hours dropping time.Drip off the back and continue reaction 3 hours under 140 ℃ of conditions of temperature of reaction, then at 140 ℃, vacuum tightness removed low boiling component 1 hour under-0.08MPa the condition, was cooled to room temperature then and obtained product.At last, 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.
The unsaturated ammonia ester of NMR spectrometry PE type polyoxy alkyl block polyether structural formula as shown in Equation 24.
Application Example 1
Prepare polycarboxylate water-reducer with the unsaturated ammonia ester Soxylat A 25-7 that makes among the preparation embodiment 1, and consider its application performance.Concrete steps are as follows:
In the round-bottomed flask of 500ml, add water at the bottom of the 210g, the big monomer of 77g, 18g vinylformic acid, 7.9g maleic anhydride, 1.9g thiohydracrylic acid, other joins ammonium persulfate solution and drips (2.5g ammonium persulphate, 30g water), the dropping time is 3 hours, temperature of reaction is 80 ± 2 ℃, reaction times is 2 hours, aging 1 hour of reaction back insulation.Be cooled to below 50 ℃ after insulation finishes, being neutralized to pH with sodium hydroxide is 6.0～7.0, obtains solid content and be 30% polycarboxylic acid series high efficiency water reducing agent.Press JG/T223-2007 " high performance water reducing agent of polyocarboxy acid " and detect, record water-reducing rate more than 27%.
Application Example 2
Prepare polycarboxylate water-reducer with the unsaturated ammonia ester EP type polyoxy alkyl block polyether that makes among the preparation embodiment 5, and consider its application performance.Concrete steps are as follows:
In the round-bottomed flask of 500ml, add water at the bottom of the 170g, the big monomer of 85g, 10g vinylformic acid, 5.9g acrylamide, 1.9g thiohydracrylic acid, other joins ammonium persulfate solution and drips (2.0g ammonium persulphate, 25g water), the dropping time is 3 hours, temperature of reaction is 80 ± 2 ℃, reaction times is 2 hours, aging 1 hour of reaction back insulation.Be cooled to below 50 ℃ after insulation finishes, being neutralized to pH with sodium hydroxide is 6.0～7.0, obtains solid content and be 35% polycarboxylic acid series high efficiency water reducing agent.Press JG/T223-2007 " high performance water reducing agent of polyocarboxy acid " and detect, record water-reducing rate more than 29%.
Although described typical embodiment for illustrative purposes, above stated specification should not be construed the restriction to this paper scope.Therefore, in the spirit and scope that do not break away from this paper, those skilled in the art can carry out various improvement, modification and replacement.
Claims (14)
1. unsaturated ammonia ester polyoxy alkyl oxide, its structural formula is shown in following formula (1):
In the 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
1Expression H or CH
3,
R
2Expression C
1-10Alkylidene group, C
6-10Arylene or C
2-10The alkylidene group that contains ester group,
R
3Expression 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。
2. the unsaturated ammonia ester polyoxy alkyl oxide of claim 1, wherein A and B are-CH
2CH
2O-, x are the integer of 5-100, and y is the integer of 5-100.
3. the unsaturated ammonia ester polyoxy alkyl oxide of claim 1, wherein A and 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.
4. the unsaturated ammonia ester polyoxy alkyl oxide of claim 1, wherein A is-CH
2CH
2O-, B is-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.
5. the unsaturated ammonia ester polyoxy alkyl oxide of claim 1, wherein A is-CH
2CH (CH
3) O-or-CH (CH
3) CH
2O-, B is-CH
2CH
2O-, x are the integer of 5-100, and y is the integer of 5-100.
6. each unsaturated ammonia ester polyoxy alkyl oxide in the claim 1～5, wherein the weight-average molecular weight of this unsaturated ammonia ester polyoxy alkyl oxide is 500～8000.
7. method for preparing each described unsaturated ammonia ester polyoxy alkyl oxide of claim 1～6, this method may further comprise the steps:
A, the alkoxyl group polyoxy alkyl oxide shown in the following formula (2) is heated to 60～140 ℃, adds the stopper of gross weight 0.01～1% then, and stir,
HO(A)
x(B)
yR
3 (2)
In the 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
3Expression 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, in the reaction system that derives from step a, drip below the unsaturated isocyanate shown in the formula (3), 0.5～4 hour dropping time, and to control temperature of reaction be 60～140 ℃, reaction pressure is 0.1～1MPa,
In the formula,
R
1Expression H or CH
3, and
R
2Expression C
1-10Alkylidene group, C
6-10Arylene or C
2-10The alkylidene group that contains ester group; And
After c, dropping finish, reaction system is continued reaction 1～3 hour under 60～140 ℃ temperature of reaction, remove low boiling component then, and be cooled to room temperature, obtain described unsaturated ammonia ester polyoxy alkyl oxide.
8. the described method of claim 7, wherein said stopper is for being selected from para benzoquinone, toluhydroquinone, thiodiphenylamine, MEHQ, trinitrobenzene, 1,1-phenylbenzene-2-trinitrophenyl-hydrazine, one or more in 2,2,6, the 6-tetramethyl piperidine oxide compound.
9. the described method of claim 7, the mol ratio of wherein said unsaturated isocyanate and described alkoxyl group polyoxy alkyl oxide is 1～1.1: 1.
10. the method for claim 7, the alkoxyl group polyoxy alkyl oxide of wherein said formula (2) is to be selected from following one or more: methoxy polyoxyethylene ether, the methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyether, methoxyl group PE type polyoxy alkyl block polyether, methoxyl group polyoxy alkyl mixes the embedding polyethers, the oxyethyl group Soxylat A 25-7, oxyethyl group polyethenoxy ether, oxyethyl group EP type polyoxy alkyl block polyether, oxyethyl group PE type polyoxy alkyl block polyether, 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 reached oxygen base polyethenoxy ether in the last of the ten Heavenly stems.
11. the method for claim 7, the unsaturated isocyanate of wherein said formula (3) is to be selected from following one or more: isocyanic acid vinyl acetate, isocyanic acid propylene ester, 3-pseudoallyl-α, α-Er Jiajibianji isocyanic ester, and methacrylic acid isocyano-ethyl ester.
12. the method for claim 10, wherein said alkoxyl group polyoxy alkyl oxide is to be selected from following one or more: methoxy polyoxyethylene ether, the methoxyl group polyethenoxy ether, methoxyl group EP type polyoxy alkyl block polyether, methoxyl group PE type polyoxy alkyl block polyether, and methoxyl group polyoxy alkyl mixes the embedding polyethers.
13. the method for claim 11, wherein said unsaturated isocyanate are isocyanic acid vinyl acetate or isocyanic acid propylene ester.
14. each described unsaturated ammonia ester polyoxy alkyl oxide application in the preparation of polycarboxylate water-reducer and polymer comb-shaped polymer in the claim 1～6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0197635A2 (en) * | 1985-04-04 | 1986-10-15 | National Starch and Chemical Investment Holding Corporation | Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein |
| US5093414A (en) * | 1987-11-10 | 1992-03-03 | Hoechst Aktiengesellschaft | Dispersion polymers based on ethylenically unsaturated monomers and containing urethane groups, process for their preparation and their use |
| US5597661A (en) * | 1992-10-23 | 1997-01-28 | Showa Denko K.K. | Solid polymer electrolyte, battery and solid-state electric double layer capacitor using the same as well as processes for the manufacture thereof |
| US5725654A (en) * | 1997-06-06 | 1998-03-10 | Arco Chemical Technology, L.P. | Cement composition |
| CN101712747A (en) * | 2009-10-27 | 2010-05-26 | 湖北德邦化工新材料有限公司 | Water-soluble system structure based on isocyanate-yl alkyl alkoxy silane and preparation method thereof |
| US20110313518A1 (en) * | 2010-06-21 | 2011-12-22 | Novartis Ag | High refractive index, acrylic ophthalmic device materials with reduced glistenings |
-
2011
- 2011-12-28 CN CN201110447641.8A patent/CN103183822B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0197635A2 (en) * | 1985-04-04 | 1986-10-15 | National Starch and Chemical Investment Holding Corporation | Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein |
| US5093414A (en) * | 1987-11-10 | 1992-03-03 | Hoechst Aktiengesellschaft | Dispersion polymers based on ethylenically unsaturated monomers and containing urethane groups, process for their preparation and their use |
| US5597661A (en) * | 1992-10-23 | 1997-01-28 | Showa Denko K.K. | Solid polymer electrolyte, battery and solid-state electric double layer capacitor using the same as well as processes for the manufacture thereof |
| US5725654A (en) * | 1997-06-06 | 1998-03-10 | Arco Chemical Technology, L.P. | Cement composition |
| CN101712747A (en) * | 2009-10-27 | 2010-05-26 | 湖北德邦化工新材料有限公司 | Water-soluble system structure based on isocyanate-yl alkyl alkoxy silane and preparation method thereof |
| US20110313518A1 (en) * | 2010-06-21 | 2011-12-22 | Novartis Ag | High refractive index, acrylic ophthalmic device materials with reduced glistenings |
Cited By (15)
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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 |
| CN104262612A (en) * | 2014-09-09 | 2015-01-07 | 江苏苏博特新材料股份有限公司 | Preparation method of ester-type polyether 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 |
| JP2017006621A (en) * | 2015-06-18 | 2017-01-12 | 明基材料股▲ふん▼有限公司 | Contact lens material, method for producing contact lens, and contact lens produced by the method |
| 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 |
| CN105778013A (en) * | 2016-03-23 | 2016-07-20 | 联泓(江苏)新材料研究院有限公司 | Polycarboxylic acid water reducer, preparation method thereof and cement admixture |
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| 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 |
| 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 |
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