WO2013131251A1 - Polyether macromonomer containing double-bond carbamate functional group and method for preparing same - Google Patents

Abstract

Disclosed are a polyether macromonomer containing a double-bond carbamate functional group and a method for preparing same. The macromonomer has the structural formula (I), in which x represents (a) or an olefin C_nH_2n, n is a natural number of 3-8, R₁, R₃, and R₄ represent H or CH₃, R₂ represents a C₁-C₁₈ alkane or aromatic hydrocarbon group, Y represents (b) or (c), and m represents the number of repeating units in a CH₂CHR₁O chain segment and is a natural number of 6-226. The method for preparing the macromonomer comprises the steps of: reacting a hydroxyl compound X-OH containing a double bond with an isocyanate to produce an intermediate, and then reacting with an alkoxy polyether to obtain a polyether macromonomer containing a double-bond carbamate. The preparation method does not need an organic solvent, can be completed in the same reaction kettle, is easy to control and has low requirements for devices. At the same time, the macromonomer has various structures and can copolymerize with many types of unsaturated monomers to obtain water-reducing agents of different molecular structures.

Description

 Polyether macromonomer containing double bond carbamate functional group and preparation method thereof

Technical field

 The invention relates to a concrete admixture intermediate and a preparation method thereof, in particular to a polyether macromonomer containing a double bond carbamate functional group and a preparation method thereof. Background technique

 The development of water reducing agent has experienced the first generation of ordinary water reducing agent represented by wood calcium, the second generation superplasticizer represented by naphthalene and melamine, and the third generation high performance represented by polycarboxylate. The process of water reducing agent. Polycarboxylate water reducing agent has been widely used due to its low dosage, high water reduction rate, good fluidity, good cement adaptability, low harmful components and good performance of hardened concrete. Polycarboxylate superplasticizers represent the future development direction of concrete admixtures due to their excellent properties and environmental friendliness. Its molecular structure design determines that the polycarboxylate water reducer can develop a series of products with different performance characteristics, meeting the requirements of modern construction engineering for the diversification of concrete materials.

 The polycarboxylate water reducing agent can be classified into a polyether type and a polyester type according to different connection modes of the branch chain and the main chain. The conventional ether type polycarboxylic acid water reducing agent is obtained by first preparing an allyl polyethylene glycol and then copolymerizing it with an unsaturated functional monomer by a free radical copolymerization method. The ester type polycarboxylic acid water reducing agent is synthesized by first synthesizing a monoalkoxy polyether, then esterifying with an unsaturated acid or an acid anhydride to prepare an unsaturated macromonomer, and synthesizing a functional monomer with a free radical copolymerization method. Polymer polycarboxylate concrete admixture.

 At present, the synthesis method of ester type polycarboxylic acid water reducing agent macromonomer is mainly carried out by using unsaturated acid (acrylic acid, methacrylic acid, etc.) and methoxypolyethylene glycol (MPEG) in a catalyst (such as concentrated sulfuric acid, p-toluene). The reaction is carried out under the action of sulfonic acid, benzenesulfonic acid, etc. to obtain an esterified macromonomer (such as the patent CN101255113A). These conventional catalysts have good catalytic effects, but the reaction time is long. The use of organic solvents such as toluene and cyclohexane as reaction solvents and water-carrying agents increases the complexity of the equipment, while the organic solvent volatilizes seriously. The low recovery rate in the process increases production costs and also pollutes the environment.

Patent CN101906209A discloses a process for synthesizing polyethylene glycol monomethacrylate with polyethylene glycol and methacrylic acid using super acid S0 ₄ ² 7Zr0 ₂ . Adding a polymerization inhibitor during the implementation, heating and refluxing, using a The water produced by benzene is more than 98%, and the water-carrying agent and the solid super acid can be recycled. However, azeotrope with cyclohexane has a cumbersome production process, high cost, and environmental pollution.

 Patent CN101333289A discloses that methacrylic acid and methoxypolyethylene glycol carry away the esterified water in a specific degree of vacuum during the esterification process, thereby pushing the reaction equilibrium to the positive direction. Although the reaction conditions are mild, no organic solvent is used, and post-treatment is eliminated, but the design requirements of the equipment are high, and the degree of vacuum reaches 0.095 to 0.099 MPa. With the use loss of the equipment, the production stability is not guaranteed. Under certain vacuum conditions, methacrylic acid is removed, the reaction material is depleted, the cost is increased, and the ratio of methacrylic acid to methoxypolyethylene glycol is changed, resulting in unstable product performance.

 The above preparation method has the disadvantages of cumbersome production process, environmental pollution caused by using organic solvent, low production efficiency, and high equipment complexity. Summary of the invention

 In order to realize the multifunctionalization of the polycarboxylate water reducing agent by molecular structure design, the present invention designs a novel polyether macromonomer containing a double bond carbamate functional group and a preparation method thereof, and the synthesis method is simple and easy to operate. , no organic solvent, less by-products, easy to achieve industrial production.

 The macromonomer structure containing the double bond urethane polyether of the present invention is as shown in (I):

Ri, R₃， R4代 表 H或 CH₃， R₂代表 〜 ₈烷烃或芳香烃，

m 代表 C ^CHR^O链段的重复单元数， m为 6〜226的自然数。 Where X

Ri, R ₃ , R4 represents H or CH ₃ , and R ₂ represents _-8 alkane or aromatic hydrocarbon,

m represents the number of repeating units of the C ^CHR^O segment, and m is a natural number of 6 to 226.

 The preparation method of the invention comprises reacting a double bond-containing hydroxy compound X-OH with an isocyanate at a certain temperature to form an intermediate, and then reacting with the alkoxy polyether to obtain a double bond urethane polyether macromonomer. Specifically, the following steps are included:

1) The hydroxy compound X-OH containing a double bond and an isocyanate are reacted at a molar ratio of 1.0:1.0 at a temperature not higher than 70 ° C to form an intermediate having the following structural formula: X

 〇■人

 NCO (ID

R ₃

 , i

， Wherein X represents o or an olefin C _n H _2n , n is a natural number from _{3 to 8} , and R ₃ and R ₄ represent H CH ₃ ,

,

 The chemical reaction formula involved in this step is as follows

X— OH OCN-Y-NCO

2) reacting the intermediate prepared in the step 1) with the alkoxy polyether at a temperature not higher than 100 ° C to obtain a double bond urethane polyether macromonomer, wherein the alkoxy polyether The molar ratio of the molar amount to the isocyanate group in the reaction system is from 1.0 to 1.1:1.0.

 In the step 1), since the isocyanate group is sensitive to water, in order to minimize the formation of reaction by-products (polyurea) and prevent the formation of gel, it is preferred to evacuate and replace the inert gas with not less than two times before the reaction, inert. The gas is preferably nitrogen, argon or helium. At the same time, the water content of the alkoxy polyether is also preferably controlled.

0.05 wt% or less.

 The double bond-containing hydroxy compound X-OH used in the present invention may be selected from the following compounds:

 1) hydroxy ester of unsaturated acid, such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, etc.;

 2) an unsaturated alcohol having a double bond at the end, such as allyl alcohol, methallyl alcohol, 3-buten-2-ol, 3-buten-1-ol, 2-methyl-3-butene- 2-alcohol, 3-methyl-3-butenol, 3-methyl-2-butenol, 4-penten-1-ol, 1-penten-3-ol, 4-pentene- 2-alcohol, 1-hexen-3-ol, 5-hexene small alcohol, 6-hepten-1-ol 1-octene-3-ol, etc.

 3) Unsaturated alcohols in which the double bond is not at the terminal: 2-butene-1-ol, 3-penten-2-ol, 2-hexen-1-ol, 2-octene-1-ol, and the like.

 In order to make the polyether macromonomer (I) have a good polymerization activity, the double bond of the hydroxy compound X-OH is preferably selected at the terminal.

The isocyanate used in the present invention requires two isocyanate groups, and the two isocyanate groups are reacted. The activity is different, which facilitates the progress of the reaction, such as toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), the two isocyanate groups have different reactivity due to the influence of steric hindrance.

 In the present invention, the molar ratio of the hydroxy compound to the isocyanate is 1.0:1.0, and the molar ratio of the alkoxypolyether to the isocyanate group in the reaction system is 1.0 to 1.1:1.0. The molar ratio of X-OH and isocyanate containing double bond hydroxy compound is controlled at 1.0:1.0, otherwise it will form a gel or affect the properties of the polyether macromonomer (I). Considering alkoxy polymerization

The ether production process results in a change in the hydroxyl content thereof, and thus the molar ratio of the alkoxy polyether to the isocyanate group in the reaction system.

An example is 1.0~1.1:1.0.

 In the present invention, the reaction temperature of the hydroxy compound and the isocyanate is preferably 40 to 70 ° C, and the reaction temperature does not exceed

 At 70 °C, the -CONH- and isocyanate groups (-NCO) of the carbamate in the intermediate (Π) continue to react to form a urea-based (-CONHCO-) structure, which is easily crosslinked into a gel. The addition of a catalyst when the intermediate (Π) and the alkoxy polyether are reacted can effectively accelerate the progress of the reaction. The catalyst may be selected from tertiary amines, organic metal salts, etc., and the amount of the catalyst is from 0.1 to 2.0% by weight based on the total weight of the reactants. The intermediate (Π) and the alkoxy polyether are reacted to form a structure (I) The temperature of the polyether macromonomer is preferably 70 to 100 °C. The temperature of the reaction in this step is not lower than 70 ° C, the temperature is too low, resulting in a long reaction time, and the polyether having a large molecular weight will be formed as a solid, affecting the reaction; the temperature is not higher than 100 ° C, otherwise the reaction is too rapid and easy to form. gel.

 The polymerization of the unsaturated double bonds can be effectively prevented from forming a gel by adding a polymerization inhibitor in the step 1). The selected polymerization inhibitor cannot react with the isocyanate group, and therefore cannot contain functional groups such as an active hydroxyl group or an amino group. Preferred polymerization inhibitors include phenothiazine, U-diphenyl-2-trinitrophenylhydrazine (DPPH), 2,2,6,6-tetramethylpiperidine nitroxyl radical (TEMPO), these groups The points can be used individually or in combination. The amount thereof is preferably from 0.1 to 2.0% by weight based on the weight of the hydroxy compound containing a double bond.

The reaction time of step 1) has a great influence on the nature of the intermediate (Π). The short time leads to incomplete reaction of the isocyanate, and the long-term formation of the urea-based structure affects the performance of the polyether macromonomer (I). During the reaction, the reaction time is generally controlled by measuring the content of isocyanate groups ("Isolation of isocyanate content in polyurethane prepolymer" HG/T2409-92). When the content of isocyanate groups reaches the required theoretical value, the reaction is completed, preferably. The reaction time is 0.5 to 3 hours. When the intermediate (Π) and the alkoxy polyether are reacted, the higher the molecular weight of the alkoxy polyether used, the lower the reactivity, and the longer the reaction time required, when isocyanic acid When the ester group content is zero, the reaction is completed, preferably 4 to 24 hours.

 The invention reacts with a hydroxy compound containing a double bond and an isocyanate to form an intermediate (11), an intermediate

(II) reacting with an alkoxy polyether to form a urethane polyether macromonomer (I) containing a double bond. The organic solvent is not used in the preparation process, it is environmentally friendly, the process is simple, the reaction is completed in the same reactor, easy to control, and the equipment requirements are low. The prepared double bond urethane polyether macromonomer has various structures, and the polyether macromonomer (I) is adjusted by selecting different double bond-containing hydroxy compounds, isocyanates, alkoxy polyether types and molecular weights. Hydrophilic and lipophilic, molecular weight. The synthesized double bond-containing urethane polyether macromonomer can be copolymerized with various unsaturated monomers to prepare a polycarboxylate water reducing agent with the same molecular structure, and a series of products with different performance characteristics are developed to satisfy Modern building engineering requirements for the diversification of concrete materials. DRAWINGS

 Figure 1 is a nuclear magnetic resonance spectrum of the product of Example 1.

 2 is an infrared spectrum diagram of the product of Example 1.

 In the examples, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, allyl alcohol, 1-octene-3-ol, 3-penten-2-ol, toluene diisocyanate (TDI) , isophorone diisocyanate (IPDI), phenothiazine, stannous octoate, dibutyltin dilaurate, triethylenediamine, 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), Alkoxy polyethers are commercially available. Example 1

52.0 g of hydroxyethyl methacrylate (0.40 mol) was added to the reaction vessel, and after evacuation, the air in the reaction flask was replaced with nitrogen three times, and 69.6 g of toluene diisocyanate TDI (0.40 mol), 0.05 g of phenothiazine was added thereto, and the temperature was raised to After stirring at 45 ° C for 1 hour with mechanical stirring, the sample was determined to have reached the theoretical value of the isocyanate group content. Add methoxypolyethylene glycol (molecular weight 2000) 800.0g (0.40mol), 0.92g of stannous octoate as catalyst (0.1%wt), and heat up to 80 °C reaction 12 after adding 110 ° C vacuum drying to remove water. Hours, cooled to 40 ° C, sampled. Nuclear magnetic resonance spectrum data of the obtained product 1H NMR (300 MHz, d ₆ -DMSO) 5 (ppm) 9.64 to 8.89 (-NHCOO-), 7.53 to 7.03 (-ArH), 6.06, 5.70 (CH ₂ = C (CH ₃ ) -COO-), 4.34 (-COOCH ₂ CH ₂ OCONH-), 3.73-3.43 (-COO(CH ₂ CH ₂ 0) _n CH ₃ -), 3.25(-OCH ₃ ), 2.13 (-ArCH ₃ ), 1.89 (CH ₂ =CCH ₃ -); Infrared data IR (KBr) vmax/cm- ¹ 3330, 2830~2965, 1730, 1600, 1540, 1470, 1340, 1280, 1240, 1110, 1059, 964, 843. Example 2

46.4 g of hydroxyethyl acrylate (0.40 mol) was added to the reaction vessel, and after evacuation, the air in the reaction flask was replaced with nitrogen three times, and 69.6 g of toluene diisocyanate TDI (0.40 mol), 0.93 g of 1,1-diphenyl- 2-Trinitrophenylhydrazine (DPPH), heated to 40 ° C, and mechanically stirred for 3 hours, sampled to determine its isocyanate group content has reached the theoretical value. Add methoxypolyethylene glycol (molecular weight 10000) 4000.0g (0.40mol), lO. lg dibutyltin dilaurate as catalyst (0.1%wt), and heat up to 70°. C was reacted for 24 hours, cooled to 40 ° C, and sampled. Nuclear magnetic resonance spectrum data of the obtained product 1H NMR (300 MHz, d ₆ -DMSO) 5 (ppm) 9.40 to 8.75 (-NHCOO-), 7.59 to 6.98 (-ArH), 6.33, 5.95 (CH ₂ =CH-COO-) , 6.14(CH ₂ =CH-COO-), 4.33 (-COOCH ₂ CH ₂ OCONH-), 3.74~ 3.43 (-COO(CH ₂ CH ₂ 0)nCH ₃ -), 3.27(-OCH ₃ ), 2.14( -ArCH ₃ ); Infrared data IR (KBr) Vmax/cm ¹ 3340, 2880~2980, 1760, 1610, 1530, 1450, 1330, 1290, 1180, 1110, 1046, 964, 811. Example 3

57.6 g of hydroxypropyl methacrylate (0.40 mol) was added to the reaction vessel, and after evacuation, the air in the reaction flask was replaced with argon three times, and 88.8 g of isophorone diisocyanate IPDI (0.40 mol), 0.10 g of phenothiazine was added. The azine was heated to 50 ° C, and after mechanical stirring for 2 hours, the sample was determined to have reached the theoretical value of the isocyanate group content. Add methoxypolypropylene glycol (molecular weight: 2000) 880.0 g (0.44 mol), 2.0 g of stannous octoate as catalyst (0.2% wt), and heat to 100 ° C for 4 hours. Cool to 40 ° C and sample. Nuclear magnetic resonance spectrum data of the obtained product 1H NMR (300MHz, d ₆ -DMSO) 5 (ppm) 8.74~8.32 (-NHCOO-), 6.07, 5.67 (CH ₂ =C(CH ₃ )COO-), 4.52~3.30

(-COOCH ₂ CH(CH ₃ )0-, -CH ₂ NH-, -CHNH, -COO(CH ₂ CH(CH ₃ )0) _n ), 3.25(-OCH ₃ ), 1.89~0.89(-CH ₃ Infrared data IR (KBr) Vmax/cm 3340, 2880, 1730, 1540, 1470, 1320, 1240, 1110, 976, 813 of the obtained product. Example 4 2.3.2 g of allyl alcohol (0.40 mol) was added to the reaction vessel. After evacuation, the air in the reaction flask was replaced with nitrogen three times, and 69.6 g of toluene diisocyanate TDI (0.40 mol) and 0.10 g of phenothiazine were added to adjust the temperature to 70 °. C. After 0.5 hours of mechanical stirring reaction, the sample was determined to have reached the theoretical value of the isocyanate group content. Add octadecyloxy polyether (molecular weight 2000) 800.0g (0.40mol), 17.8g catalyst triethylenediamine (2.0%wt), and heat up to 90 °C after adding 110 ° C vacuum to remove water. 24 hours, cooled to 40 ° C, sampled. Nuclear magnetic resonance spectrum data of the obtained product 1H NMR (300 MHz, d ₆ -DMSO) 5 (ppm) 9.52 8.80 (-NHCOO-), 7.52 6.98 (-ArH), 5.95 (CH ₂ =CH-), 5.29, 5.18 (CH ₂ =CH-CH ₂ 0-), 4.15(CH ₂ =CH-CH ₂ 0-) 3.74-3.43 (-COO(CH ₂ CH ₂ 0)„CH ₃ , -OCH ₂ CH ₂ -),

2.14(-ArCH ₃ ), 1.57 1.27(-(CH ₂ ) ₁₆ CH ₃ ), 0.88 ( -CH ₂ CH ₃ ) ; Infrared data IR (KBr) Vmax/cm ¹ 3330, 2890 3000 1750, 1590, 1510 1440 1350, 1280, 1240, 1200, 1110 1000 856 Example 5

 51.2 g of 1-octene-3-ol (0.40 mol) was added to the reaction vessel, and after evacuation, the air in the reaction flask was replaced with nitrogen three times, and 69.6 g of toluene diisocyanate TDI (0.40 mol) and 0.10 g of phenothiazine were added. After adjusting the temperature to 60 ° C and mechanically stirring for 1 hour, the sample was determined to have reached the theoretical value of the isocyanate group content. Phenol-based polyethylene glycol (molecular weight 2000) 800.0g after adding water and vacuum drying in advance at 110 ° C

(0.40 mol), 0.92 g of stannous octoate as a catalyst (0.1% by weight), and the mixture was heated to 100 ° C for 10 hours, cooled to 40 ° C, and sampled. Nuclear magnetic resonance spectrum data of the obtained product 1H NMR (300MHz, d ₆ -DMSO) 5 (ppm) 9.63 8.89 (-NHCOO-), 7.54 6.80 (-ArH), 5.80 (C3⁄4=CH-), 5.23, 5.10 (CH ₂ =CH-), 4.12(-CH(OH)-CH=CH ₂ ), 3.73-3.43 (-COO(CH ₂ CH ₂ 0) _n -), 2.11(-ArCH ₃ ), 1.49 1.17(-(CH _{2 4} CH ₃ ), 0.89 ( -CH ₂ CH ₃ ) ; infrared data IR (KBr) v /cm 3340, 2890,

 1750, 1600 1540 1470, 1350, 1254, 1220, 1110 964 843, 811 Example 6

34.4 g of 3-penten-2-ol (0.40 mol) was added to the reaction vessel, and after evacuation, the air in the reaction flask was replaced with nitrogen three times, and 69.6 g of toluene diisocyanate TDI (0.40 mol), 0.10 g of phenothiazine was added. After raising the temperature to 45 ° C and mechanically stirring for 1 hour, the sample was determined to have reached the theoretical value of the isocyanate group content. Join in advance Methoxy polyethylene glycol (molecular weight 2000) SOO.Og (0.40 mol), 1.04 g of stannous octoate as catalyst (0.1% wt), and heated to 85 ° C for 10 hours after vacuum drying at 110 ° C. , Cool to 40 ° C, sample. Nuclear magnetic resonance spectrum data of the obtained product NMR (300 MHz, d ₆ -DMSO) 6 (ppm) 9·32 to 8.65 (-NHCOO-), 7.54 to 7.00 (-ArW), 5.63, 5.52 (CH ₃ CH=CH-) , 4.24 (=CH-CH(OH)-), 3.75~3.40 (-COO(CW ₂ C y ₂ O) _n -), 3.25(-OCH ₃ ), 2.13 (-ArCH ₃ ), 1.68, 1.23 (- CW ₃ ); Infrared data IR (KBr) vmax/cm- ¹ 3320, 2860~2985, 1730, 1660, 1600, 1540, 1470, 1330, 1280, 1240, 1100, 1060, 968, 860.

Claims

Claim 1. A polyether macromonomer comprising a double bond carbamate functional group, characterized in that the macromonomer has the structural formula:

 3 R  , / Wherein X represents or the olefin C _n H _2n , n is a natural number from _{3 to 8} , R ₃ , R 4 represents H or CH ₃ , R ₂ represents a ~C ₁₈ alkane or an aromatic hydrocarbon, and Y represents ^^\ or , / m The number of repeating units representing the CTtCHRiO segment is a natural number from 6 to 226.  2. The method for preparing a polyether macromonomer having a double bond carbamate functional group according to claim 1, comprising the steps of:  1) The hydroxy compound X-OH containing a double bond and an isocyanate are reacted at a molar ratio of 1.0:1.0 at a temperature of not higher than 70 ° C to form an intermediate having the following structural formula: X-O Which represents H or CH ₃ ,

 2) reacting the intermediate prepared in the step 1) with the alkoxy polyether at a temperature not higher than 10 CTC to obtain a double bond urethane polyether macromonomer, wherein the molar amount of the alkoxy polyether is The molar ratio of isocyanate groups in the reaction system is from 1.0 to 1.1:1.0.  3. Process according to claim 2, characterized in that step 2) is carried out in the presence of a catalyst in an amount of from 0.1 to 2.0% by weight based on the total weight of the reactants. 4. Process according to claim 3, characterized in that the catalyst is selected from the group consisting of tertiary amines or organometallic salts. 5. Process according to claim 1 or 2 or 3, characterized in that the double bond of the hydroxy compound X-OH is at the end.  6. Process according to claim 1 or 2 or 3, characterized in that the isocyanate used has two isocyanate groups which differ in reactivity.  7. Process according to claim 1 or 2 or 3, characterized in that the isocyanate is selected from the group consisting of toluene diisocyanate or isophorone diisocyanate.  The method according to claim 1 or 2 or 3, wherein the reaction temperature of the step 1) is 40 to 70 ° C, and the reaction temperature of the step 2) is 70 to 100 ° C.  9. A method according to claim 1 or 2 or 3, characterized in that the reaction time of step 1) is from 0.5 to 3 hours. The reaction time of step 2) is 4 to 24 hours.  10. A method according to claim 1 or 2 or 3, characterized in that in step 1) a polymerization inhibitor is added to prevent the polymerization of unsaturated double bonds to form a gel, and the optional polymerization inhibitor comprises phenothiazine. 1,1-diphenyl-2-trinitrophenylhydrazine or 2,2,6,6-tetramethylpiperidine nitroxyl radical, these components are used singly or in any ratio, and the amount thereof is contained The weight of the double bond hydroxy compound is 0.1 to 2.0%.