CN103183822B - A kind of unsaturated ammonia ester polyoxyalkyl ether and preparation method thereof - Google Patents

Abstract

Disclosed is an unsaturated urethane polyoxyalkyl ether used in a polycarboxylate water reducer and a preparation method thereof. The unsaturated urethane polyoxyalkyl ether has a structure shown in formula (1), and the definitions of symbols in the formula are as shown in the description. The unsaturated urethane polyoxyalkyl ether is prepared by reacting alkoxy polyoxyalkyl ether and unsaturated isocyanate under certain temperature, pressure and the presence of a polymerization inhibitor. The unsaturated urethane polyoxyalkyl ether of the present invention has high stability and has high reactivity terminal double bonds at the same time, so it can be used to prepare comb-shaped polymers and polycarboxylate water reducers.

Description

A kind of unsaturated urethane polyoxyalkyl ether and preparation method thereof

technical field

The present invention relates to a kind of unsaturated urethane polyoxyalkyl ether and preparation method thereof, more specifically, the present invention relates to a kind of unsaturated urethane polyoxygen used in the preparation of polycarboxylate water reducer and comb polymer Alkyl ethers and methods for their preparation.

Background technique

As an indispensable building material today, concrete has entered the era of commercialization and high performance. The commercialization and high performance of concrete are realized by concrete admixtures, among which the most critical variety is water reducing agent, which accounts for more than 80% of the total admixture dosage. The polycarboxylate superplasticizer with a comb-shaped molecular structure has become an indispensable component in the preparation of high-performance concrete because of its low dosage, high water-reducing rate, and good slump maintenance. The degree of freedom is large, the synthesis method is diverse, and the potential for high performance is great, so it has become the focus of research and development at home and abroad in recent years.

Polycarboxylate superplasticizer is an important comb-type polymer, which is usually synthesized by copolymerization of unsaturated polyoxyalkyl ether macromonomer and unsaturated carboxylic acid small molecule monomer under the action of an initiator. of. The alkenyl groups of large and small monomers form a vinyl main chain through copolymerization, and the polyoxyalkylene segments of polyoxyalkyl ether macromonomers form comb-shaped side chains. Among them, unsaturated polyoxyalkyl ether macromonomers It accounts for almost 80% of the total mass of polycarboxylate superplasticizer dry agent. It can be seen that unsaturated polyoxyalkyl ether macromonomer is a vital basic raw material for the superplasticizer industry.

Disclosed in CN101531747A is a method for preparing polycarboxylate water reducer, using acrylic acid and methoxypolyoxyethylene ether for esterification to obtain unsaturated carboxylic acid ester polyoxyethylene ether, which is used to prepare polycarboxylate water reducer agent. However, the disadvantages of the unsaturated carboxylic acid ester polyoxyethylene ether macromonomer are: the preparation process requires a dehydration step, the process is complicated, the esterification is incomplete, and many by-products are generated at the same time, resulting in unstable product quality; poor storage stability .

Biopolymer, Volume 10, 29-95 (2003), discloses the preparation of terminal ethylenically unsaturated polyoxyethylene ether macromonomers by reacting alkenyl alcohol as an initiator with ethylene oxide, i.e. alkenyl ether type polyoxyethylene Alkyl ether macromonomer. This type of alkenyl ether type macromonomer is connected by ether bonds, so the chemical properties are stable, and at the same time, there is no esterification process, which simplifies the synthesis process. However, the polymerization activity of alkenyl ether macromonomers is low, and it is difficult to achieve uniform polymerization, resulting in uneven distribution of side chains of comb polymers, thereby affecting their application properties.

Contents of the invention

In order to solve the above problems, the present invention provides an unsaturated urethane polyoxyalkyl ether, which has a double bond with high reactivity, and uses urethane groups to connect polyoxyethylene ether chains, which greatly improves the efficiency of unsaturated urethane polyoxyalkylene ethers. Storage and use stability of alkyl ethers. When unsaturated urethane polyoxyalkyl ether is used to prepare comb polymer, it can be well copolymerized with unsaturated small monomers such as acrylic acid, methacrylic acid, maleic anhydride, styrene and sodium methacrylic sulfonate. , can well adjust the density of polyoxyalkyl ether side chains to achieve good dispersion application performance.

In addition, the present invention also provides a method for preparing the unsaturated urethane polyoxyalkyl ether. This preparation method has simple steps, high double bond retention rate, high degree of urethanization of the product, and can well control its molecular structure. and molecular weight.

On the one hand, the present invention provides a kind of unsaturated urethane polyoxyalkyl ether, and its structural formula is as shown in following formula (1):

In the formula,

A is -CH ₂ CH(CH ₃ ) O- or -CH(CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ O-,

B is -CH ₂ CH(CH ₃ ) O- or -CH(CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ O-,

R ₁ represents H or CH ₃ ,

R ₂ represents a C _1-10 alkylene group, a C _6-10 arylene group or a C _2-10 ester-containing alkylene group,

R ₃ represents C _1-10 alkyl,

x is expressed as an integer from 0-100,

y is represented as an integer from 0-100, and

10≤x+y≤150.

On the other hand, A and B in the above-mentioned unsaturated urethane polyoxyalkyl ether are both -CH ₂ CH ₂ O-, x is an integer of 5-100, and y is an integer of 5-100, which is called unsaturated ammonia Ester polyoxyethylene ether.

On the other hand, A and B in the above-mentioned unsaturated urethane polyoxyalkyl ether are both -CH ₂ CH(CH ₃ )O- or -CH(CH ₃ )CH ₂ O-, x is an integer of 5-100 , y is an integer of 5-100, called unsaturated urethane polyoxypropylene ether.

On the other hand, A in the above-mentioned unsaturated urethane polyoxyalkyl ether is -CH ₂ CH ₂ O-, B is -CH ₂ CH(CH ₃ )O- or -CH(CH ₃ )CH ₂ O-, x is an integer of 5-100, and y is an integer of 5-100, which is called unsaturated urethane EP type polyoxyalkylene block polyether.

In another aspect, A in the above-mentioned unsaturated urethane polyoxyalkyl ether is -CH ₂ CH(CH ₃ )O- or -CH(CH ₃ )CH ₂ O-, B is -CH ₂ CH ₂ O-, x is an integer of 5-100, and y is an integer of 5-100, which is called unsaturated urethane PE type polyoxyalkylene block polyether.

In another aspect, both A and B in the above-mentioned unsaturated urethane polyoxyalkyl ether are -CH ₂ CH ₂ O- or -CH ₂ CH(CH ₃ )O- or -CH(CH ₃ )CH ₂ O- , x is an integer of 5-100, and y is an integer of 5-100, which is called unsaturated urethane polyoxyalkylene embedded polyether.

In yet another aspect, the above-mentioned unsaturated urethane polyoxyalkyl ether of the present invention has a weight average molecular weight of 500-8000.

In addition, the present invention also provides a method for preparing the above-mentioned unsaturated urethane polyoxyalkyl ether, the method comprising the steps of:

a. Heat the alkoxypolyoxyalkyl ether shown in the following formula (2) to 60-140°C, then add 0.01-1% of the total weight inhibitor, and stir evenly,

HO(A) _x (B) _y R ₃ (2)

In the formula,

A is -CH ₂ CH(CH ₃ ) O- or -CH(CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ O-,

B is -CH ₂ CH(CH ₃ ) O- or -CH(CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ O-,

R ₃ represents C _1-10 alkyl,

x is expressed as an integer from 0-100,

y is represented as an integer from 0-100, and

10≤x+y≤150;

b. Add dropwise the unsaturated isocyanate shown in the following formula (3) to the reaction system obtained from step a, the dropwise addition time is 0.5-4 hours, and the reaction temperature is controlled to be 60-140° C., and the reaction pressure is 0.1-1 MPa,

In the formula,

R ₁ represents H or CH ₃ , and

R ₂ represents a C _1-10 alkylene group, a C _6-10 arylene group or a C _2-10 ester-containing alkylene group; and

c. After the dropwise addition, continue to react the reaction system at a reaction temperature of 60-140°C for 1-3 hours, then remove low-boiling components and cool down to room temperature to obtain the unsaturated urethane polyoxyalkylene ether. The reaction mechanism of preparing unsaturated urethane polyoxyalkylene ether is shown in reaction formula (4):

On the one hand, in the method of the present invention, the unsaturated isocyanate is one or more selected from the following: vinyl isocyanate, allyl isocyanate, 3-isopropenyl-α, α-dimethyl benzyl isocyanate, and isocyanoethyl methacrylate, preferably vinyl isocyanate and/or allyl isocyanate.

On the other hand, in the method of the present invention, the alkoxy polyoxyalkyl ether is one or more selected from the following: methoxypolyoxyethylene ether, methoxypolyoxypropylene ether, methyl Oxygen EP type polyoxyalkylene block polyether, methoxyl PE type polyoxyalkylene block polyether, methoxypolyoxyalkylene hybrid embedded polyether, ethoxy polyoxyethylene ether, ethoxy Polyoxypropylene ether, ethoxy EP type polyoxyalkyl block polyether, ethoxy PE type polyoxyalkyl block polyether, ethoxy polyoxyalkyl hybrid polyether, isopropoxy polyether Oxyethylene ether, butoxypolyoxyethylene ether, decyloxypolyoxyethylene ether, decyloxypolyoxyethylene ether, preferably methoxypolyoxyethylene ether, methoxypolyoxypropylene ether, methoxy EP type Polyoxyalkylene block polyether, methoxy PE type polyoxyalkylene block polyether, and methoxypolyoxyalkylene hybrid embedded polyether.

On the other hand, in the method of the present invention, the polymerization inhibitor is selected from p-benzoquinone, methylhydroquinone, phenothiazine, p-hydroxyanisole, aromatic nitro compounds and other polymerization inhibitors one or more species.

In another aspect, in the method of the present invention, the molar ratio of the unsaturated isocyanate to the alkoxypolyoxyalkyl ether is 1˜1.1:1.

As used herein, the term "arylene group" means that the benzene ring contains double substituents, and the term "unsaturated urethane EP type polyoxyalkylene block polyether" means that the unsaturated urethane group is first combined with polyoxyethylene A compound that is linked with an ether segment and then linked with a polyoxypropylene ether segment; the term "unsaturated urethane PE type polyoxyalkylene block polyether" means that the unsaturated urethane group is first linked with a polyoxypropylene ether segment Compounds that are then linked to polyoxyethylene ether segments; the term "unsaturated urethane polyoxyalkylene hetero-embedded polyether" refers to the disordered arrangement of unsaturated urethane groups with oxyethylene ether segments and oxypropylene ether segments compound of.

Compared with the alkenyl-terminated polyoxyethylene ethers in the prior art, the unsaturated urethane polyoxyalkylene ethers prepared by the present invention have high stability and have high-reactivity terminal double bonds, which can be used to prepare comb-shaped polymerization and polycarboxylate superplasticizers.

In order to better understand the present invention, hereinafter, the present invention will be described more specifically with reference to the following examples. Unless otherwise specified herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods and following examples mentioned therein are illustrative only and are not intended to limit the scope of the invention.

Description of drawings

Fig. 1 is the NMR spectrogram of unsaturated urethane polyoxyethylene ether.

detailed description

The following examples are given to illustrate the present invention more specifically, but the present invention is not limited thereto.

In one embodiment, the present invention provides an unsaturated urethane polyoxyalkyl ether, which is prepared by the reaction of alkoxy polyoxyalkyl ether and unsaturated isocyanate, with a weight average molecular weight of 500-8000 ; Wherein, the structural formula of alkoxy polyoxyalkylene is as shown in formula (5):

HO(A) _x (B) _y R ₃ (5)

In formula (5), A is -CH ₂ CH(CH ₃ )O- or -CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ O-, B is -CH ₂ CH(CH ₃ )O- or -CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ O-, R ₃ represents C _1-10 alkyl, wherein x represents an integer of 0-100, y represents an integer of 0-100, and 10≤x+y≤150;

The structural formula of unsaturated isocyanate is shown in formula (6):

In formula (6), R ₁ represents H or CH3, R ₂ represents C _1-10 alkylene, C _6-10 arylene or C _2-10 ester-containing alkylene.

In a specific embodiment, the alkoxy polyoxyalkyl ether is methoxy polyoxyethylene ether, methoxy polyoxypropylene ether, methoxy EP type polyoxyalkyl block polyether, methyl Oxygenated PE type polyoxyalkylene block polyether, methoxypolyoxyalkylene mixed embedded polyether, ethoxylated polyoxyethylene ether, ethoxylated polyoxypropylene ether, ethoxylated EP type polyoxyalkylene Block polyether, ethoxylated PE type polyoxyalkylene block polyether, ethoxypolyoxyalkylene hybrid polyether, isopropoxypolyoxyethylene ether, butoxypolyoxyethylene ether, decyl oxide Base polyoxyethylene ether, decyloxypolyoxypropylene ether, preferably methoxypolyoxyethylene ether, methoxypolyoxypropylene ether, methoxy EP type polyoxyalkylene block polyether, methoxy PE type Polyoxyalkylene block polyether, methoxypolyoxyalkylene hybrid embedded polyether. When the unsaturated urethane polyoxyalkyl ether containing polyoxyethylene ether chain is used to prepare polycarboxylate water reducer, it has high water reducing rate and slump retention performance; containing polyoxyalkylene block polyether chain When the unsaturated urethane polyoxyalkyl ether with polyoxyalkylene embedded polyether chain and polyoxypropylene ether chain is used to prepare polycarboxylate water reducer, it has good water reducing rate and low foam performance. Can be used to prepare concrete with special properties. The aforementioned alkoxypolyoxyalkyl ethers are commercially available. For example, methoxypolyoxyethylene ether is commercially available from Liaoning Aoke Chemical Co., Ltd. under the trade name MPEG1000.

In a specific embodiment, the unsaturated isocyanate is vinyl isocyanate, allyl isocyanate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, and isocyanoethyl methacrylate One of the esters, preferably vinyl isocyanate and allyl isocyanate. The above-mentioned monomer C is commercially available. For example, vinyl isocyanate is commercially available from sigma-aldrich.

In a specific embodiment, the unsaturated urethane polyoxyalkyl ether preferably has a molecular weight of 500-8000. When the molecular weight of unsaturated urethane polyoxyalkyl ether is lower than 500, the side chain of the prepared polycarboxylate water reducer is too short, the dispersibility is poor, and the water reducing rate is low; when the molecular weight of unsaturated urethane polyoxyalkyl ether When the molecular weight is greater than 8000, the side chain of the prepared polycarboxylate water reducer is too long, which will cause the side chains to intertwine, reduce the dispersion performance, and reduce the water reducing rate.

In another embodiment, the present invention provides a kind of method for preparing unsaturated urethane polyoxyalkyl ether, the method comprises the steps:

a. Heat the alkoxypolyoxyalkyl ether shown in the following formula (7) to 60-140°C, then add 0.01-1% of the total weight inhibitor, and stir evenly,

HO(A) _x (B) _y R ₃ (7)

In the formula,

A is -CH ₂ CH(CH ₃ ) O- or -CH(CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ O-,

B is -CH ₂ CH(CH ₃ ) O- or -CH(CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ O-,

R ₃ represents C _1-10 alkyl,

x is expressed as an integer from 0-100,

y is represented as an integer from 0-100, and

10≤x+y≤150;

b. Add dropwise the unsaturated isocyanate shown in the following formula (8) to the reaction system obtained from step a, the dropwise addition time is 0.5-4 hours, and the reaction temperature is controlled to be 60-140° C., and the reaction pressure is 0.1-1 MPa,

In the formula,

R ₁ represents H or CH ₃ , and

R ₂ represents a C _1-10 alkylene group, a C _6-10 arylene group or a C _2-10 ester-containing alkylene group; and

c. After the dropwise addition, continue to react the reaction system at a reaction temperature of 60-140°C for 1-3 hours, then remove low-boiling components and cool down to room temperature to obtain the unsaturated urethane polyoxyalkylene ether.

In a specific embodiment, the polymerization inhibitor used in the present invention is p-benzoquinone, methylhydroquinone, phenothiazine, p-hydroxyanisole, trinitrobenzene, 1,1-diphenyl-2- One or more of trinitrophenylhydrazine and 2,2,6,6-tetramethylpiperidine oxide. The above-mentioned polymerization inhibitors are commonly used initiators known in the art and can be purchased from the market.

In a specific embodiment, the molar ratio of unsaturated isocyanate to alkoxy polyoxyalkyl ether used in the present invention is 1-1.1:1.

In an embodiment of the present invention, if the temperature is too low, the alkoxypolyoxyalkyl ether is in a solid state, and it is difficult to react with the unsaturated isocyanate; if the temperature is too high, side reactions are likely to occur. Therefore, the preferable reaction temperature is 60-140 degreeC.

Considering the influence of the order of addition and the speed of addition on the preparation of unsaturated urethane polyoxyalkyl ethers, in embodiments of the present invention, preferably unsaturated isocyanate is added to alkoxy polyoxyalkyl ethers, and preferably at 0.5～ The dropwise addition was completed within 4 hours. When the dropping speed is too fast, the reaction of the material is too intense, and the reaction temperature should not be controlled; when the dropping speed is too slow, the production efficiency will be affected.

In the embodiment of the present invention, preferably after the dropwise addition is completed, the reactant is continued to react at a temperature of 60-140° C. for 1-3 hours, so as to fully proceed the reaction, which is beneficial to improve the utilization rate of raw materials.

In an embodiment of the present invention, in order to ensure the complete reaction of the alkoxy polyoxyalkyl ether, the unsaturated isocyanate is slightly excessive. Therefore, after the reaction is completed, the unsaturated isocyanate is removed under reduced pressure to obtain the unsaturated urethane polyoxygen Alkyl ether.

The synthesis operations of the unsaturated urethane polyoxyalkyl ethers are all carried out under a dry nitrogen environment. Various reactants are used for synthesis reaction after drying and dehydration.

Preparation Example 1

Weigh 400.00g of methoxypolyoxyethylene ether (the structural formula is shown in formula 9), add it into the reaction bottle and raise the temperature to 60°C and start stirring, then add 0.43g of phenothiazine and stir evenly, then drop in 30.29g of vinyl isocyanate Esters, the reaction is carried out at 60°C, 0.2MPa, and the dropwise addition time is 1 hour. After dropping, continue to react for 2 hours at a reaction temperature of 60°C, then remove low-boiling components at 60°C and a vacuum of -0.08MPa for 1 hour, and then cool to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis (at 30° C., using polyethylene glycol as a standard product to convert the molecular weight), the number average molecular weight is 512 g/mol, and the weight average molecular weight is 532 g/mol. The DAWNHELEOS II type produced by Wyatt Company and the OHpakSB-802.5HQ gel chromatography column produced by Shodex Company were used for the determination. In the following examples, when measuring at 30°C, it is all carried out under this condition.

The structural formula of unsaturated urethane polyoxyethylene ether determined by NMR spectrum is shown in formula 10, and the NMR spectrum is shown in accompanying drawing 1. In the measurement, INOVA400M manufactured by Varian was used.

Preparation Example 2

Weigh 400.00g of ethoxy PE-type polyoxyalkylene block polyether (structural formula shown in formula 11), add it into the reaction bottle and heat up to 130°C and start stirring, then add 0.61g of benzoquinone and stir evenly, then drop in 5.09 g vinyl isocyanate, the reaction is carried out at 130°C, 0.8MPa, and the dropping time is 0.6 hours. After dropping, continue to react for 2.5 hours at a reaction temperature of 130°C, then remove low boiling point components at 130°C and a vacuum of -0.08MPa for 1 hour, and then cool to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis, the number average molecular weight was 5442 g/mol, and the weight average molecular weight was 5503 g/mol.

The structural formula of the unsaturated urethane PE type polyoxyalkylene block polyether determined by NMR spectroscopy is shown in Formula 12.

Preparation Example 3

Weigh 400.00g of methoxypolyoxyalkyl intercalated polyether (the structural formula is shown in formula 13), add it into the reaction bottle and raise the temperature to 100°C and start stirring, then add 0.33g of methyl hydroquinone and stir evenly, then drop in 10.69 g propylene isocyanate, the reaction is carried out at 100°C, 0.2MPa, and the dropwise addition time is 2 hours. After dropping, continue to react for 1.5 hours at a reaction temperature of 100°C, then remove low boiling point components at 100°C and a vacuum of -0.08MPa for 1 hour, and then cool to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis, the number average molecular weight was 3209 g/mol, and the weight average molecular weight was 3250 g/mol.

The structural formula of the unsaturated urethane polyoxyalkyl intercalated polyether determined by NMR spectroscopy is shown in Formula 14.

Preparation Example 4

Weigh 400.00g of isopropoxypolyoxypropylene ether (the structural formula is shown in formula 15), add it into the reaction bottle and raise the temperature to 80°C and start stirring, then add 0.82g of p-hydroxyanisole and stir evenly, then drop 12.41g of iso Propylene cyanate, the reaction is carried out at 80°C, 0.2MPa, and the dropwise addition time is 1 hour. After dropping, continue to react for 3 hours at a reaction temperature of 80°C, then remove low boiling point components at 80°C and a vacuum of -0.08MPa for 1 hour, and then cool to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis, the number average molecular weight was 2742 g/mol, and the weight average molecular weight was 2776 g/mol.

The structural formula of unsaturated urethane polyoxypropylene ether determined by NMR spectroscopy is shown in formula 16.

Preparation Example 5

Weigh 400.00g of methoxy EP type polyoxyalkylene block polyether (structural formula is shown in formula 17), add it into the reaction bottle and raise the temperature to 120°C to start stirring, then add 0.44g of benzoquinone and stir evenly, then drop in 38.15 g3-isopropenyl-α,α-dimethylbenzyl isocyanate, the reaction is carried out at 120°C, 0.4MPa, and the dropwise addition time is 1 hour. After the drop, the reaction was continued for 1.5 hours at a reaction temperature of 120°C, and then at 120°C and a vacuum of -0.08MPa, the low boiling point components were removed for 1 hour, and then cooled to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis, the number average molecular weight was 2327 g/mol, and the weight average molecular weight was 2341 g/mol.

The structural formula of the unsaturated urethane EP type polyoxyalkylene block polyether determined by NMR spectroscopy is shown in Formula 18.

Preparation Example 6

Weigh 400.00g of butoxy polyoxyalkyl intercalated polyether (the structural formula is shown in formula 19), add it into the reaction bottle and raise the temperature to 70°C, start stirring, then add 1.05g of benzoquinone and stir evenly, then drop 23.48g of formazan Base isocyanoethyl acrylate, the reaction is carried out at 100°C, 0.1MPa, and the dropping time is 3 hours. After dropping, continue to react for 2.5 hours at a reaction temperature of 100°C, then remove low boiling point components at 100°C and a vacuum of -0.08MPa for 1 hour, and then cool to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis, the number average molecular weight was 2673 g/mol, and the weight average molecular weight was 2691 g/mol.

The structural formula of the unsaturated urethane polyoxyalkylene embedded polyether determined by NMR spectroscopy is shown in Formula 20.

Preparation Example 7

Weigh 400.00g of decyloxypolyoxyethylene ether (the structural formula is shown in formula 21), add it into the reaction bottle and raise the temperature to 90°C and start stirring, then add 0.61g of benzoquinone and stir evenly, then drop in 11.73g of vinyl isocyanate , the reaction was carried out at 90°C, 0.3MPa, and the dropping time was 4 hours. After the drop, the reaction was continued for 2 hours at a reaction temperature of 90°C, and then at 90°C and a vacuum of -0.08MPa, the low boiling point components were removed for 1 hour, and then cooled to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis, the number average molecular weight was 2401 g/mol, and the weight average molecular weight was 2430 g/mol.

The structural formula of the unsaturated urethane polyoxyethylene ether determined by NMR spectroscopy is shown in formula 22.

Preparation Example 8

Weigh 400.00g of methoxy PE type polyoxyalkylene block polyether (the structural formula is shown in formula 23), add it into the reaction bottle and raise the temperature to 140°C to start stirring, then add 0.61g of benzoquinone and stir evenly, then drop in 4.45 g propylene isocyanate, the reaction is carried out at 140°C, 0.4MPa, and the dropping time is 1.5 hours. After dropping, continue to react for 3 hours at a reaction temperature of 140°C, then remove low boiling point components at 140°C and a vacuum of -0.08MPa for 1 hour, and then cool to room temperature to obtain the product. Finally, the product is analyzed by means of NMR spectroscopy and GPC measurements.

According to GPC analysis, the number average molecular weight is 7580 g/mol, and the weight average molecular weight is 7620 g/mol.

The structural formula of the unsaturated urethane PE type polyoxyalkylene block polyether determined by NMR spectroscopy is shown in formula 24.

Application Example 1

The polycarboxylate water reducer was prepared with the unsaturated urethane polyoxyethylene ether prepared in Preparation Example 1, and its application performance was considered. Specific steps are as follows:

Add 210g of bottom water, 77g of macromonomer, 18g of acrylic acid, 7.9g of maleic anhydride, 1.9g of mercaptopropionic acid into a 500ml round bottom flask, add ammonium persulfate solution dropwise (2.5g of ammonium persulfate, 30g of water) , The dropping time is 3 hours, the reaction temperature is 80±2°C, the reaction time is 2 hours, and the aging time is 1 hour after the reaction. After the heat preservation is completed, the temperature is lowered to below 50° C., neutralized with sodium hydroxide to a pH of 6.0 to 7.0, and a polycarboxylic acid-based high-efficiency water reducer with a solid content of 30% is obtained. According to JG/T223-2007 "Polycarboxylate High Performance Water Reducer", the measured water reduction rate is above 27%.

Application Example 2

The polycarboxylate water reducer was prepared with the unsaturated urethane EP type polyoxyalkylene block polyether prepared in Example 5, and its application performance was considered. Specific steps are as follows:

Add 170g of bottom water, 85g of macromonomer, 10g of acrylic acid, 5.9g of acrylamide, 1.9g of mercaptopropionic acid in a 500ml round bottom flask, add ammonium persulfate solution dropwise (2.0g of ammonium persulfate, 25g of water), The dropping time is 3 hours, the reaction temperature is 80±2°C, the reaction time is 2 hours, and the aging time is 1 hour after the reaction. After the heat preservation is completed, the temperature is lowered to below 50° C., neutralized with sodium hydroxide to a pH of 6.0 to 7.0, and a polycarboxylic acid-based high-efficiency water reducer with a solid content of 35% is obtained. According to JG/T223-2007 "Polycarboxylate High Performance Water Reducer", the measured water reduction rate is above 29%.

While exemplary embodiments have been described for purposes of illustration, the foregoing description should not be construed as limiting the scope of the disclosure. Therefore, various improvements, modifications, and substitutions may be made by those skilled in the art without departing from the spirit and scope herein.

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.