CN108250429B

CN108250429B - Anti-clay phosphate superplasticizer with low relative molecular weight, preparation method and application thereof

Info

Publication number: CN108250429B
Application number: CN201611236904.XA
Authority: CN
Inventors: 刘加平; 冉千平; 亓帅; 王涛; 马建峰; 范士敏; 舒鑫; 曹攀攀
Original assignee: Jiangsu Bote New Materials Co Ltd
Current assignee: Jiangsu Bote New Materials Co Ltd
Priority date: 2016-12-28
Filing date: 2016-12-28
Publication date: 2020-10-23
Anticipated expiration: 2036-12-28
Also published as: CN108250429A

Abstract

The invention provides a low relative molecular weight anti-clay phosphate superplasticizer, a preparation method and application thereof. The preparation method comprises the following steps: (1) polyamine with a specific structure is taken as an initiator, an alkylene oxide ring-opening reaction is carried out, and a branched polyether polyamine intermediate with a hydroxyl end group is obtained after purification; (2) the hydroxyl-terminated phosphate of the branched polyether polyamine is esterified and purified to obtain the anti-clay phosphate superplasticizer with low relative molecular weight; the molecular weight of the low relative molecular weight clay-resistant phosphate superplasticizer is 5000-14000.

Description

Anti-clay phosphate superplasticizer with low relative molecular weight, preparation method and application thereof

Technical Field

The invention relates to a low-relative-molecular-weight clay-resistant phosphate superplasticizer, a preparation method and application thereof, belonging to the technical field of concrete admixtures.

Background

With the rapid development of the infrastructure construction of China, the number of the currently-built expressways, railways, large bridges, tunnels, large hydraulic and hydroelectric projects, high-rise buildings and underground projects all dominate the world. None of these major projects has been associated with concrete materials and put higher demands on properties such as strength and durability of concrete. The addition of the high-performance polymer dispersant into the concrete is the most effective, economic and simple technical approach for reducing the cement consumption, improving the utilization rate of industrial waste residues and realizing the high durability and performance improvement of the concrete. Among them, the polycarboxylate superplasticizer is more and more widely used in concrete engineering as a contemporary high-performance water reducer, but theoretical research and engineering application show that the polycarboxylate superplasticizer has compatibility problems with concrete raw materials such as admixture, cement, sulfate, clay mineral on the surface of aggregate, and the like. In particular, the clay minerals in the sand not only reduce the strength and durability of the concrete and increase the drying shrinkage of the concrete, but also have very remarkable influence on the workability of the concrete doped with the polycarboxylic acid water reducing agent. In addition, along with the rapid increase of the construction amount of the current society, the consumption of the sandstone is huge, high-quality sandstone aggregate is more and more in short supply, and the adaptability problem of the clay mineral and the polycarboxylic acid water reducing agent is increasingly highlighted.

The adaptability problem between the clay and the polycarboxylate water reducer seriously affects the working performance of the concrete, experts and scholars at home and abroad have consistent opinions on the reasons for the influence of the clay on the polycarboxylate water reducer, and the clay is considered to be mainly used for adsorbing a large amount of polycarboxylate water reducer, so that the effective water reducer molecules in slurry are reduced, and the workability of the concrete is affected. At present, a common method for solving the adaptability problem of clay minerals in concrete is to increase the addition amount of a polycarboxylic acid water reducing agent or additionally add a sacrificial agent, but the cost of the concrete is greatly increased, and the later strength of the concrete is influenced by the excessive addition amount of an additive, and the setting time of the concrete is possibly too long. Therefore, it is necessary to develop a high efficiency water reducing agent with good mud resistance to meet the engineering requirements.

In order to solve the problem of concrete compatibility, engineering technicians and researchers introduce phosphate groups with high adsorbability from the level of water reducing agent molecule construction based on certain research theories. On one hand, the tolerance of the water reducing agent to calcium ions in a cement paste system is improved, and on the other hand, the phosphate group has stronger charge attraction than carboxyl.

Patent document WO2010/040611 a1 discloses a method for producing a linear condensation type water reducing agent having a phosphoric acid group. It is prepared by condensation reaction of esterification product of ethylene glycol phenyl ether and phosphoric acid, formaldehyde and polyoxyethylene monophenyl ether at 105 ℃. The water reducing rate and the retentivity of the straight-chain type condensation water reducing agent synthesized by the method are relatively poorer than those of a comb-shaped polycarboxylic acid water reducing agent.

Patent document FR2696736A reports a class of small molecule sewage treatment agents. In the patent, they use polyether amine as raw material, and utilize its terminal amino group to produce Mannich reaction, and the terminal is hypophosphorylated, and then the corresponding phosphite product is obtained. The micromolecules can be used as micromolecule water reducing agents, and have the defects that the cost of raw material polyether amine is high, and the dispersing and mud resisting effects are not ideal due to the fact that the molecular weight of products is small and the number of adsorption groups is small.

Patent document US20140039098a1 discloses a method for synthesizing a diphosphate based water reducing agent. Prepared by the reaction of polyethylene glycol monomethyl ether, polyacrylic acid and hydroxyethylidene diphosphonic acid under the conditions of 175 ℃ and 20mBar vacuum degree. Although the diphosphonate water reducing agent has certain sulfate ion resistance and clay resistance, the method has long reaction time, harsh industrial conditions, low esterification yield and high investment on early industrial production equipment.

Chinese patent document CN 103467670A reports a preparation method of an anti-clay polycarboxylate water reducer containing phosphate groups. The water reducing agent is prepared by copolymerizing isopentenol polyoxyethylene ether, quaternary ammonium salt oligomer, aminotrimethylene phosphoric acid, unsaturated carboxylic acid and the like. The water reducer is insensitive to the mud content of concrete aggregate, and can solve the problems of low water reducing rate, large slump loss, low strength and the like of concrete under the condition of not increasing the mixing amount of the water reducer. Patent documents CN103641963A, CN 104031217A, CN 105236806a also disclose the clay-resistant performance of similar water reducing agents containing phosphoric acid groups. However, the preparation method of the water reducing agent generally comprises the steps of firstly preparing the unsaturated monomer containing the phosphate group, and then synthesizing the unsaturated monomer through free radical polymerization copolymerization, so that the possibility of changes of the structure, the molecular weight and the like of the water reducing agent exists, the structure and the molecular weight of the water reducing agent cannot be accurately controlled, and meanwhile, the operation steps are complicated and the process control is difficult.

The above patent documents disclose different anti-clay type phosphate water reducing agents, but the effect is not very ideal, and the preparation process is relatively complex and the industrialization conditions are harsh, so it is necessary to develop a phosphoric acid type water reducing agent with a more novel structure, which not only can maintain the good working performance of concrete, but also can be prepared simply and effectively.

Disclosure of Invention

Object of the Invention

The invention aims to provide a low-relative-molecular-weight clay-resistant phosphate superplasticizer which has excellent clay-resistant performance, and the preparation method of the phosphate superplasticizer is simple and convenient to operate, mild in reaction conditions, capable of being industrially produced and free of environmental pollution.

Another object of the present invention is to provide a process for the preparation of the above low relative molecular weight anti-clay type phosphate superplasticizers.

It is another object of the present invention to provide the use of said low relative molecular weight clay-resistant phosphate superplasticizers as cement dispersants.

Summary of The Invention

In a first aspect of the present invention, there is provided a process for the preparation of a low relative molecular weight clay-resistant phosphate superplasticizer comprising the steps of:

(1) polyamine is taken as an initiator, and an alkylene oxide ring-opening reaction is carried out, so that a branched polyether polyamine intermediate with a hydroxyl end group is obtained after purification;

(2) the hydroxyl-terminated phosphate of the branched polyether polyamine is esterified and purified to obtain the anti-clay phosphate superplasticizer with low relative molecular weight;

the polyamine is unsubstituted macrocyclic polyamine of C5-C16, or the structural formula is shown as (I),

wherein the content of the first and second substances,

r is C2-C10 alkylene, C6-C10 cycloalkylene, C6-C15 arylene or C2-C40 alkylene containing at least one heteroatom of nitrogen, oxygen and sulfur, C6-C10 cycloalkylene or C6-C15 arylene,

r 'and R' are H or alkyl of C1-C2;

the alkylene oxide has 2 to 24 carbon atoms;

the molecular weight of the low relative molecular weight clay-resistant phosphate superplasticizer is 5000-14000.

Preferably, R is C2-C6 alkylene, C6-C10 cycloalkylene, C6-C15 arylene, or C2-C40 alkylene, C6-C10 cycloalkylene or C6-C15 arylene with heteroatom nitrogen. More preferably, R is C2-C6 alkylene, C6-C10 cycloalkylene, C6-C15 arylene, or C2-C40 alkylene having a heteroatom nitrogen, and the polyamine is, for example, ethylenediamine, 1, 3-propylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, spermine, spermidine, isophoronediamine, 1, 2-cyclohexyldiamine, 1, 3-cyclohexyldiamine, 1, 4-cyclohexyldiamine, 1, 3-cyclohexyldimethylamine, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 1, 4-phenylenediamine, 2, 6-tolylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, diethyltoluenediamine, 1, 2-naphthylenediamine, 1, 4-naphthylenediamine, 1, 3-naphthylenediamine, 1, 4-phenylenediamine, 1, 5-naphthalenediamine, 1, 8-naphthalenediamine, 2, 3-naphthalenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, linear polyethyleneimine having a molecular weight of 600 to 800, or macrocyclic polyamine having a molecular weight of C6 to C10 (e.g., C8).

The alkylene, cycloalkylene or aralkylene group having a hetero atom means that hydrogen or carbon of the alkylene, cycloalkylene or aralkylene group is substituted with a hetero atom.

The unsubstituted macrocyclic polyamines of the present invention are a well-known and common class of chemical materials, and have the structure of a cyclic structure formed by the spaced connection of ethylene and secondary amino groups.

Preferably, the alkylene oxide has 2 to 6 carbon atoms; more preferably, the alkylene oxide is at least one of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, 2-methyl-1, 2-propylene oxide, 1, 2-cyclopentane oxide, 2-methyl-1, 2-butylene oxide, tetrahydrofuran, 3-methyl-1, 2-butylene oxide, 1, 2-hexane oxide, and 2, 3-hexane oxide. Further preferably, the alkylene oxide is ethylene oxide, or a mixture containing propylene oxide and/or ethylene oxide, and when the alkylene oxide is a mixture containing propylene oxide and ethylene oxide, the molar ratio of propylene oxide to ethylene oxide is (0.7-1.2): 1.

the ring-opening reaction of the alkylene oxide is well known in the art, and is generally performed by: under certain temperature and pressure conditions, polyamine and alkylene oxide react under the action of a ring-opening polymerization catalyst, after a period of reaction, the reaction temperature is kept, vacuum is carried out under reduced pressure to remove volatile substances, insoluble substances are removed by filtration, and a branched polyether polyamine intermediate is obtained. The detailed steps and conditions are not described herein. If a mixture of more than two alkylene oxides is used, the polyether segments obtained can be controlled in random or block form and the arrangement order of the various polyether segments by controlling the feeding manner. This is not a particular requirement of the present invention.

Preferably, in the step (2),

the phosphorylation reaction takes strong acid cation resin as a catalyst;

the terminal hydroxyl group of the branched polyether polyamine intermediate and a phosphorylation reagent are subjected to phosphorylation reaction according to the molar ratio of 1 (1.05-1.2),

the phosphorylation reagent is phosphoric acid, polyphosphoric acid, phosphorus pentoxide, pyrophosphoric acid, tripolymetaphosphoric acid or tetrapolymetaphosphoric acid.

The branched polyether polyamine intermediate skeleton based on the esterification reaction substrate contains a plurality of tertiary amine groups, and meanwhile, more hydroxyl groups needing phosphorylation are needed, the efficiency of the traditional phosphorylation method is not high, a strong acid cation resin is introduced into the reaction as a catalyst for the first time, a strong acid group in the catalyst can be complexed with a tertiary amine group, the loss of a phosphorylation reagent is avoided, the post-treatment is simple, the catalyst can be filtered out only by filtering, and the whole reaction phosphorylation efficiency is improved. It is worth noting that the cationic resin can be recycled after being activated by sulfuric acid, and is simple and efficient. Such strong acid cation resins are commercially available, for example, as used in the examples of the present invention under the designation NKC-9 or Amberlyst-15.

Preferably, the mass of the strong acid cation resin is 1-5% of that of the branched polyether polyamine intermediate; the phosphorylation reaction is carried out at 60-100 ℃ and-0.05-0.1 MPa, and the reaction time is 2-6 h.

After the end of the phosphorylation reaction, the purification method is well known in the art, and the specific operation can be as follows: the reaction temperature was maintained, and the reaction mixture was evacuated under reduced pressure to remove volatile substances and filtered to remove insoluble substances. The obtained product can be directly used as an overspeed agent, or can be used by adding alkali for neutralization and then adding water for dilution to a certain concentration for storage and transportation. The final concentration is generally from 30 to 40% by weight.

In a second aspect of the present invention, there is also provided a low relative molecular weight clay-resistant phosphate superplasticizer obtained according to the above preparation method.

In a third aspect of the invention, there is also provided the use of the low relative molecular weight anti-clay type phosphate superplasticizers obtained according to the above preparation process as additives for aqueous dispersions of hydraulic binders and/or latent hydraulic binders.

For hydraulic binders, these superplasticizers are used as additives for mixtures based on cement, lime, gypsum or anhydrite or on these components, preferably cement. The latent hydraulic binder is typically present in the form of a pozzolan, fly ash or blast furnace slag.

From 0.01% to 10% by weight, in particular from 0.05% to 5% by weight, based on the mass of the hydraulic binder used, expressed as pure solids. The superplasticizer is used as a flow agent or a water reducing agent.

The invention has the beneficial effects that:

(1) phosphate groups are introduced into the structure of the water reducing agent as adsorption groups, and bidentate phosphoric acid has stronger coordination capacity and can be more quickly adsorbed to the surface of cement particles, so that the adaptability problem of the existing water reducing agent and clay is favorably solved.

(2) The star-shaped water reducer has a three-dimensional structure, and is difficult to be adsorbed and intercalated into a layered structure of clay, so that the quantity of the water reducer for dispersing cement particles is not remarkably reduced, the negative influence of the clay on the performance of the water reducer can be greatly reduced, and the adaptability of the water reducer to various sandstone aggregates is effectively improved.

(3) The process has the advantages of low cost of selected raw materials, simple and efficient preparation by adopting a one-pot method for synthesis, continuous operation in the same reaction kettle, contribution to improving the reaction efficiency and shortening the reaction time, and realization of industrial large-scale production.

Detailed Description

The invention is described in detail below by way of examples, which are merely illustrative and do not represent a limitation on the scope of the invention, the drugs or reagents used in the examples are all available from the Aladdin reagent company, the catalyst NaH is 60% pure, and the other reagents are more than 98% pure.

In the examples of the present invention, the number average molecular weight of the polymer was measured by Wyatt technology corporation gel permeation chromatography. (gel column: Shodex SB806+803 two chromatographic columns in series; eluent: 0.1M NaNO₃A solution; velocity of mobile phase: 0.8 ml/min; and (3) injection: 20 μ l of 0.5% aqueous solution; a detector: a refractive index detector of Shodex RI-7 type; standard substance: polyethylene glycol GPC standard (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232).

Example 1

The branched polyether polyamine, the synthetic initiator of which is ethylenediamine, the polymerization monomer of which is ethylene oxide, and the catalyst NaH (60 wt%) added in an amount (based on 100% purity) of 0.8% of the amount of the ethylenediamine material. 0.1mol (6.0g) of ethylenediamine, 11.3mol (497.2g) of ethylene oxide and 32mg of NaH (60 wt%) as a catalyst were weighed out. Adding the initiator ethylenediamine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 110 ℃ to initiate reaction, continuously introducing the residual ethylene oxide, keeping the temperature for reaction for 1h, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain a branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.05, weighing 5.1g of NKC-9 and 49.6g (0.42mol) of 85 percent phosphoric acid, adding the weighed materials into the reaction kettle, keeping the reaction temperature at 60 ℃ and the reaction pressure between-0.05 and-0.1 MPa, and continuing to react for 2 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 10% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight is 5228 and the molecular weight distribution is 1.21 through GPC (gel permeation chromatography) test.

Example 2

The branched polyether polyamine has 1, 3-propane diamine as initiator, ethylene oxide as monomer and sodium hydroxide as catalyst in 1.5% of the 1, 3-propane diamine. 0.1mol (7.4g) of 1, 3-propanediamine, 24.7mol (1086.8g) of ethylene oxide and 60mg of sodium hydroxide as a catalyst were weighed out. Adding the initiator 1, 3-propane diamine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 110 ℃ to initiate reaction, continuously introducing the residual ethylene oxide, keeping the temperature for reaction for 3 hours, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.05, weighing 10.9g amberlyst-15 and 49.6g (0.42mol) 85% phosphoric acid, adding into the reaction kettle, keeping the reaction temperature of 80 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 2 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing to pH 7 by using a NaOH solution with the mass concentration of 15%, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown water reducing agent finished product, and testing by GPC (gel permeation chromatography) to obtain the water reducing agent with the molecular weight of 11024 and the molecular weight distribution of 1.44.

Example 3

The branched polyether polyamine has 1, 2-phenylenediamine as initiator, propylene oxide as monomer and Na as catalyst in 1.6 wt%. 0.1mol (10.8g) of 1, 2-phenylenediamine, 17.5mol (1016.4g) of propylene oxide and 37mg of catalyst Na were weighed out. Adding the initiator 1, 2-phenylenediamine and a catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of propylene oxide, heating to 110 ℃ to initiate reaction, continuously introducing the residual propylene oxide, keeping the temperature for reaction for 5 hours, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain a branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.1, weighing 20.5g of NKC-9 and 82.1g (0.44mol) of 76% polyphosphoric acid, adding into the reaction kettle, keeping the reaction temperature of 90 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 2 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing to pH 7 by using a NaOH solution with the mass concentration of 15%, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 10432 and the molecular weight distribution of the finished water reducing agent is 1.39 through GPC (gel permeation chromatography).

Example 4

The branched polyether polyamine is synthesized by using pentaethylenehexamine as a synthetic initiator, propylene oxide as a polymerization monomer and NaH (wt 60%) as a catalyst, wherein the addition amount of the NaH is 1.5% of the amount of the pentaethylenehexamine. 0.1mol (23.2g) of pentaethylenehexamine, 12.6mol (731.8g) of propylene oxide and 35mg of catalyst Na were weighed out. Adding the initiator pentaethylenehexamine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of propylene oxide, heating to 120 ℃ to initiate reaction, continuously introducing the residual propylene oxide, keeping the temperature for reaction for 5 hours, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.8mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.1, weighing 22.6g of NKC-9 and 79.9g (0.88mol) of phosphorus pentoxide, adding into the reaction kettle, keeping the reaction temperature at 100 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 4 hours. And after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 15% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 7381 and the molecular weight distribution of the finished water reducing agent is 1.30 through GPC (gel permeation chromatography) test.

Example 5

The branched polyether polyamine has 1, 4-butanediamine as initiator, ethylene oxide and propylene oxide as monomer, and sodium methoxide as catalyst in 1.2% of the 1, 4-butanediamine. 0.1mol (8.8g) of 1, 4-butanediamine, 8.6mol (378.4g) of ethylene oxide, 7.9mol (458.9g) of propylene oxide and 65mg of sodium methoxide as a catalyst were weighed out. Adding the initiator 1, 4-butanediamine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 110 ℃ to initiate reaction, continuously introducing the residual ethylene oxide and the residual propylene oxide in turn, keeping the temperature for reaction for 3 hours, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.05, weighing 42.3g amberlyst-15 and 49.6g (0.42mol) 85% phosphoric acid, adding into the reaction kettle, keeping the reaction temperature at 90 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 4 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 20% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight is 8506 and the molecular weight distribution is 1.36 according to GPC (gel permeation chromatography) tests.

Example 6

The branched polyether polyamine, the synthetic initiator of 1, 2-cyclohexanediamine, the polymerization monomers of ethylene oxide, propylene oxide and 1, 2-epoxycyclopentane, and the addition amount (calculated by 100 percent purity) of the catalyst NaH (wt60 percent) of 1.6 percent of the amount of the 1, 2-cyclohexanediamine substance. 0.1mol (11.4g) of 1, 2-cyclohexanediamine, 9.4mol (413.6g) of ethylene oxide, 7.9mol (458.9g) of propylene oxide, 5.2mol (437.4g) of 1, 2-epoxycyclopentane and 64mg of NaH (wt. 60%) as a catalyst were weighed out. Adding the initiator 1, 2-cyclohexanediamine and a catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 130 ℃ to initiate reaction, sequentially and continuously introducing the rest of ethylene oxide, propylene oxide and 1, 2-epoxycyclopentane, keeping the temperature for reaction for 6 hours, reducing the pressure to remove volatile substances, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate with the block structure.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.2, 26.6g of amberlyst-15 and 85.4g (0.48mol) of pyrophosphoric acid are weighed and added into the reaction kettle, the reaction temperature is kept at 100 ℃ and the reaction pressure is kept between-0.05 and-0.1 MPa, and the reaction is continued for 6 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 30% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the mass concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 13582 and the molecular weight distribution of the finished water reducing agent is 1.51 through GPC (gel permeation chromatography) test.

Example 7

The branched polyether polyamine, the synthetic initiator of 1, 2-cyclohexanediamine, the polymerization monomers of ethylene oxide, propylene oxide and 1, 2-epoxycyclopentane, and the addition amount (calculated by 100 percent purity) of the catalyst NaH (wt60 percent) of 1.6 percent of the amount of the 1, 2-cyclohexanediamine substance. 0.1mol (11.4g) of 1, 2-cyclohexanediamine, 9.4mol (413.6g) of ethylene oxide, 7.9mol (458.9g) of propylene oxide, 5.2mol (437.4g) of 1, 2-epoxycyclopentane and 64mg of NaH (wt. 60%) as a catalyst were weighed out. Adding the initiator 1, 2-cyclohexanediamine and a catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 130 ℃ to initiate reaction, introducing a mixture of the rest of ethylene oxide, propylene oxide and 1, 2-epoxycyclopentane, keeping the temperature for reaction for 6 hours, reducing the pressure to remove volatile substances, and filtering to remove insoluble substances to obtain a branched polyether polyamine intermediate with a random structure.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.2, 26.6g of amberlyst-15 and 85.4g (0.48mol) of pyrophosphoric acid are weighed and added into the reaction kettle, the reaction temperature is kept at 100 ℃ and the reaction pressure is kept between-0.05 and-0.1 MPa, and the reaction is continued for 6 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 10% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 13623 and the molecular weight distribution of the finished water reducing agent is 1.64 through GPC (gel permeation chromatography) test.

Example 8

The branched polyether polyamine has 1, 4-naphthalene diamine as initiator, propylene oxide and 1, 2-epoxy hexane as polymerization monomer and Na as catalyst in 2% of 1, 4-naphthalene diamine. 0.1mol (15.8g) of 1, 4-naphthalenediamine, 10.2mol (592.4g) of propylene oxide, 4.6mol (460.7g) of 1, 2-epoxyhexane and 46mg of Na catalyst were weighed out. Adding the initiator 1, 4-naphthalene diamine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of propylene oxide, heating to 130 ℃ to initiate reaction, sequentially and continuously introducing the residual propylene oxide and 1, 2-epoxycyclohexane, keeping the temperature for reaction for 5 hours, reducing the pressure to remove volatile substances, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.2, weighing 21.4g of amberlyst-15 and 76.8g (0.48mol) of trimetaphosphoric acid, adding into the reaction kettle, keeping the reaction temperature at 100 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 4 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 20% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 10592 and the molecular weight distribution is 1.52 by GPC (GPC).

Example 9

The branched polyether polyamine has triethylene tetramine as initiator, ethylene oxide and tetrahydrofuran as monomer and potassium hydroxide as catalyst in 2% of the amount of triethylene tetramine. 0.1mol (14.6g) of triethylene tetramine, 8.5mol (372.6g) of ethylene oxide, 5.6mol (403.8g) of tetrahydrofuran and 112mg of catalyst potassium hydroxide are weighed. Adding the initiator triethylene tetramine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 120 ℃ to initiate reaction, continuously introducing the rest of ethylene oxide and tetrahydrofuran in sequence, keeping the temperature for reaction for 4 hours, reducing the pressure to remove volatile substances, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.6mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.1, weighing 23.7g of NKC-9 and 76.1g (0.66mol) of 85 percent phosphoric acid, adding into the reaction kettle, keeping the reaction temperature at 100 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 6 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 10% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight is 7695 and the molecular weight distribution is 1.33 according to GPC (gel permeation chromatography) test.

Example 10

Branched polyether polyamine, the synthesis initiator is linear polyethyleneimine (Mr 600), the polymerization monomers are ethylene oxide and propylene oxide, and the catalyst NaH (wt. 60%) is added in an amount (calculated by 100% purity) of 1.5% of the amount of the polyethyleneimine material. 0.1mol (60.0g) of polyethyleneimine, 16.9mol (742.6g) of ethylene oxide, 10.4mol (602.8g) of propylene oxide and 60mg of NaH catalyst were weighed out. Adding the initiator polyethyleneimine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 120 ℃ to initiate reaction, continuously introducing the residual ethylene oxide and the residual propylene oxide in sequence, keeping the temperature for reaction for 5 hours, reducing the pressure to remove volatile substances, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (1.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.1, weighing 70.3g of NKC-9 and 139.8g (1.54mol) of phosphorus pentoxide, adding into the reaction kettle, keeping the reaction temperature at 100 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 6 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 20% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 13295 and the molecular weight distribution is 1.67 through GPC (gel permeation chromatography) test.

Example 11

Branched polyether polyamine, wherein the synthetic initiator is macrocyclic tetramine (molecular formula is C)₈N₄H₂₀) The polymerized monomers are ethylene oxide, propylene oxide and 2, 3-butylene oxide, and the catalyst isThe amount of sodium methoxide added is 1.4% of the amount of macrocyclic tetramine material. 0.1mol (17.2g) of macrocyclic tetramine, 8.1mol (356.1g) of ethylene oxide, 8.5mol (492.5g) of propylene oxide, 4.0mol (288.4g) of 2, 3-butylene oxide and 76mg of sodium methoxide serving as a catalyst are weighed. Adding the initiator macrocyclic tetramine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 130 ℃ to initiate reaction, continuously introducing the rest of ethylene oxide, propylene oxide and 2, 3-butylene oxide in sequence, keeping the temperature for reaction for 6 hours, reducing the pressure to remove volatile substances, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.1, weighing 46.2g of amberlyst-15 and 82.1g (0.44mol) of 76 percent polyphosphoric acid, adding the weighed materials into the reaction kettle, keeping the reaction temperature of 100 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 5 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing to pH 7 by using a NaOH solution with the mass concentration of 15%, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 11693 and the molecular weight distribution of the finished water reducing agent is 1.61 through GPC (gel permeation chromatography) test.

Comparative example 1

The branched polyether polyamine is synthesized by n-butylamine as a synthetic initiator, ethylene oxide and propylene oxide as polymerization monomers, and the addition amount of sodium methoxide serving as a catalyst is 1.2 percent of the amount of the n-butylamine substance. 0.1mol (7.3g) of n-butylamine, 8.6mol (378.4g) of ethylene oxide, 7.9mol (458.9g) of propylene oxide and 65mg of sodium methoxide as a catalyst were weighed out. Adding the initiator n-butylamine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 60-70 ℃ to initiate reaction, continuously heating to 110 ℃, continuously introducing the residual ethylene oxide and the residual propylene oxide in sequence, keeping the temperature for reaction for 3 hours, reducing the pressure to remove volatile substances, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.2mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.05, weighing 25.4g amberlyst-15 and 24.8g (0.21mol) 85% phosphoric acid, adding into the reaction kettle, keeping the reaction temperature of 80 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 4 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 20% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight is 8270 and the molecular weight distribution is 1.28 according to GPC (gel permeation chromatography) test.

Comparative example 2

The branched polyether polyol has the synthesis initiator of glycerol, the polymerization monomers of ethylene oxide and propylene oxide, and the addition amount of sodium methoxide serving as a catalyst is 2 percent of that of glycerol. 0.1mol (9.2g) of glycerol, 10.2mol (448.8g) of ethylene oxide, 9.5mol (551.8g) of propylene oxide and 108mg of sodium methoxide as a catalyst were weighed. Adding the initiator glycerol and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 110 ℃ to initiate reaction, continuously introducing the residual ethylene oxide and the residual propylene oxide in sequence, keeping the temperature for reaction for 3 hours, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain the branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.3mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.1, weighing 40.1g of NKC-9 and 30.0g (0.33mol) of phosphorus pentoxide, adding into the reaction kettle, keeping the reaction temperature at 90 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 5 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 20% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 10238 and the molecular weight distribution is 1.45 by GPC (GPC).

Comparative example 3

Branched polyether polyamine, the synthesis initiator is ethylenediamine, the polymerization monomer is ethylene oxide, and the catalyst NaH (wt 60%) is added in an amount (in 100% purity) of 0.8% of the amount of ethylenediamine. 0.1mol (6.0g) of ethylenediamine, 10.6mol (466.4g) of ethylene oxide and 32mg of NaH (wt. 60%) as a catalyst were weighed out. Adding the initiator ethylenediamine and the catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 110 ℃ to initiate reaction, continuously introducing the residual ethylene oxide, keeping the temperature for reaction for 1h, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain a branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.05, weighing 10.2g NKC-9 and 49.6g (0.42mol) 85% phosphoric acid, adding into the reaction kettle, keeping the reaction temperature at 60 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 2 h. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 10% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 4593 and the molecular weight distribution of the finished water reducing agent is 1.18 through GPC (gel permeation chromatography) test.

Comparative example 4

The branched polyether polyamine, the synthetic initiator of 1, 2-cyclohexanediamine, the polymerization monomers of ethylene oxide, propylene oxide and 1, 2-epoxycyclopentane, and the addition amount (calculated by 100 percent purity) of the catalyst NaH (wt60 percent) of 1.6 percent of the amount of the 1, 2-cyclohexanediamine substance. 0.1mol (11.4g) of 1, 2-cyclohexanediamine, 10.2mol (448.8g) of ethylene oxide, 8.7mol (505.3g) of propylene oxide, 6.5mol (546.8g) of 1, 2-epoxycyclopentane and 64mg of NaH (wt. 60%) as a catalyst were weighed out. Adding the initiator 1, 2-cyclohexanediamine and a catalyst into a closed reaction kettle, vacuumizing to-0.1 MPa, introducing 20g of ethylene oxide, heating to 130 ℃ to initiate reaction, sequentially and continuously introducing the rest of ethylene oxide, propylene oxide and 1, 2-epoxycyclopentane, keeping the temperature for reaction for 6 hours, removing volatile substances under reduced pressure, and filtering to remove insoluble substances to obtain a branched polyether polyamine intermediate.

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.2, weighing 75.6g amberlyst-15 and 85.4g (0.48mol) pyrophosphoric acid, adding into the reaction kettle, keeping the reaction temperature at 100 ℃ and the reaction pressure between-0.05 and-0.1 MPa, and continuing to react for 6 hours. And (3) after the reaction is finished, reducing the pressure, vacuumizing to remove volatile substances, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 30% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the mass concentration of 30% to obtain a brown water reducing agent finished product, and testing by GPC (gel permeation chromatography) that the molecular weight is 14869 and the molecular weight distribution is 1.74.

Comparative example 5

The molar ratio of alcoholic hydroxyl group (0.4mol) of intermediate of branched polyether polyamine to phosphorylating reagent is 1: 1.05, weighing 49.6g (0.42mol) of 85 percent phosphoric acid, adding the phosphoric acid into the reaction kettle, keeping the reaction temperature of 90 ℃ and the reaction pressure of-0.05 to-0.1 MPa, and continuing to react for 4 hours. And (3) after the reaction is finished, removing volatile substances by vacuum pumping under reduced pressure, filtering to remove insoluble substances, neutralizing by using a NaOH solution with the mass concentration of 20% until the pH value is about 7, adding water to dilute to a water reducing agent solution with the concentration of 30% to obtain a brown finished water reducing agent, wherein the molecular weight of the finished water reducing agent is 8155 and the molecular weight distribution of the finished water reducing agent is 1.52 through GPC (gel permeation chromatography) test. Molecular weight test results show that the phosphorylation efficiency of the esterified polyether polyamine intermediate is very low without adding a catalyst, and almost no phosphorylation is caused due to steric hindrance.

Application example

The application effect of the prepared anti-clay phosphate water reducing agent is inspected through the fluidity of the mortar. Wherein the cement adopts two kinds of cement with different brands and specifications: the cement is characterized in that the cement and the sea snail P.II 52.5 cement in the small open field in the south of the Yangtze river are respectively mixed at the test temperature of 25 ℃, the test sand adopts ISO standard sand, the ash-sand ratio is 1:1.6, the clay adopts a typical mixture of montmorillonite and kaolin, the montmorillonite and the kaolin are mixed according to the mass ratio of 1:1, the mixing amount is calculated according to the mass of the sand, and the phosphate water reducing agent is calculated according to the bending solid amount by taking the mass of the cement as a reference. The clay resistance of the water reducing agent is inspected through the initial fluidity of the mortar, and the test results are as follows:

TABLE 1 mortar fluidity test in Small open-field Cement (water reducing agent content 0.2%, water cement ratio 0.35)

TABLE 2 mortar fluidity test in sea snail cements (water reducing agent content 0.3%, water cement ratio 0.35)

The experimental results show that the phosphate water reducing agent prepared by the method disclosed by the invention has a certain molecular weight range (the fact that the water reducing agent has a small molecular size and is easy to be adsorbed and intercalated into a layered structure of clay, and the clay anti-clay effect is not obvious) from polyamine (the fact that the molecular weight is too small means that the water reducing agent has a large molecular size and prevents the water reducing agent from being adsorbed to the surface of cement particles, so that the water reducing performance of the water reducing agent is weakened, and meanwhile, the phosphorylation efficiency in the preparation process of the water reducing agent plays a vital role in the activity of the water reducing agent).

Claims

1. A preparation method of a low relative molecular weight clay-resistant phosphate superplasticizer is characterized by comprising the following steps:

the polyamine is C5-C16 unsubstituted macrocyclic polyamine_，Or the structural formula is shown as (I),

wherein the content of the first and second substances,

r 'and R' are independently H or alkyl of C1-C2;

the alkylene oxide has 2 to 24 carbon atoms;

the molecular weight of the low relative molecular weight clay-resistant phosphate superplasticizer is 5000-14000;

in the step (2), the step (c),

the phosphorylation reaction takes strong acid cation resin as a catalyst,

2. The process for the preparation of a low relative molecular weight clay-resistant phosphate superplasticizer of claim 1,

the alkylene oxide has 2 to 6 carbon atoms.

3. The process for the preparation of a low relative molecular weight clay-resistant phosphate-based superplasticizer of claim 2,

the alkylene oxide is at least one of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, 2-methyl-1, 2-propylene oxide, 1, 2-cyclopentane oxide, 2-methyl-1, 2-butylene oxide, tetrahydrofuran, 3-methyl-1, 2-butylene oxide, 1, 2-hexane oxide and 2, 3-hexane oxide.

4. The process for the preparation of a low relative molecular weight clay-resistant phosphate-based superplasticizer of claim 3,

the alkylene oxide is ethylene oxide, propylene oxide or a mixture containing propylene oxide and ethylene oxide,

when the alkylene oxide is a mixture containing propylene oxide and ethylene oxide, the molar ratio of propylene oxide to ethylene oxide is (0.7-1.2): 1.

5. the process for the preparation of a low relative molecular weight clay-resistant phosphate superplasticizer of claim 1,

r is C2-C6 alkylene, C6-C10 cycloalkylene, C6-C15 arylene, or C2-C40 alkylene with heteroatom nitrogen, C6-C10 cycloalkylene or C6-C15 arylene.

6. The method of preparing a low relative molecular weight clay-resistant phosphate superplasticizer of claim 5,

the polyamine is ethylenediamine, 1, 3-propylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, spermine, spermidine, isophoronediamine, 1, 2-cyclohexyldiamine, 1, 3-cyclohexyldiamine, 1, 4-cyclohexyldiamine, 1, 3-cyclohexyldimethylamine, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 1, 4-phenylenediamine, 2, 6-toluenediamine, 2,4, 6-trimethyl-m-phenylenediamine, diethyl-toluenediamine, 1, 2-naphthalenediamine, 1, 4-naphthalenediamine, 1, 5-naphthalenediamine, 1, 8-naphthalenediamine, 2, 3-naphthalenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, Polyethylene polyamine, linear polyethyleneimine with the molecular weight of 600-800 or macrocyclic polyamine with the molecular weight of C6-C10.

7. The method of preparing a low relative molecular weight anti-clay phosphate superplasticizer of claim 1, wherein the mass of said strongly acidic cationic resin is 1% to 5% of the branched polyether polyamine intermediate; the phosphorylation reaction is carried out at 60-100 ℃ and-0.05-0.1 MPa.

8. A low relative molecular weight clay-resistant phosphate superplasticizer obtained by the process of any one of claims 1 to 7.

9. Use of the anti-clay phosphate superplasticizers of low relative molecular weight obtained by the preparation process according to any one of claims 1 to 7 as additives for aqueous dispersions of hydraulic binders and/or latent hydraulic binders.