CN109627940B - Polyurea resin composition and preparation method and construction method thereof - Google Patents

Abstract

The invention provides a polyurea resin composition which comprises the following components in parts by weight: the component A comprises: 40-70 parts of isocyanate, 30-60 parts of pigment and filler and 1-5 parts of auxiliary agent I; the component B comprises: 20-40 parts of organic amine curing agent, 60-80 parts of pigment and filler and 0-5 parts of auxiliary agent II; when in use, the component A and the component B are mixed according to the volume ratio of 1-1.3: 1. The invention also provides a preparation method and a construction method of the polyurea resin composition. The polyurea resin composition has good adhesive force with a base layer, can be sprayed for the second time, is suitable for high-pressure spraying or airless spraying, is not sensitive to humidity, and can be sprayed continuously, so that a continuous and integrated lining repairing material is formed on the inner wall of a pipeline, and the polyurea resin composition does not contain a solvent, is safe and environment-friendly.

Description

Polyurea resin composition and preparation method and construction method thereof

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a polyurea resin composition, and a preparation method and a construction method thereof.

Background

The pipe repair can be classified into an excavation repair technique and a non-excavation repair technique according to whether excavation is performed. The excavation and restoration are that an excavating machine is used for excavating ditches, and the ditches are backfilled after the pipelines are restored or replaced, so that the method is suitable for places with low population density, wide construction places and relatively small influence on traffic. However, with the development of cities, the arrangement of underground water supply pipelines is complicated, the load of urban roads is more and more serious, the construction difficulty is high by adopting an excavation repair technology, the excavation repair technology is unrealistic, and a lot of adverse effects are caused to the society and the environment. The trenchless repairing technology has the advantages of small facility for the surrounding environment and the road surface, short construction period and convenient operation, and the paint is directly and uniformly coated on the inner wall of the original pipeline by utilizing the aerodynamic principle to form a new lining protective layer.

The pipeline spraying repair material comprises an epoxy spraying material, a polyurethane spraying material and a polyurea spraying material. The epoxy spraying material takes epoxy resin as a main film forming substance, adopts two components or a single component for spraying, has the advantages of good adhesive force with the inner wall of the pipeline, but only can spray a thin film coating and has poor aging performance; the polyurethane spraying material mainly takes aromatic polyurethane as a main body, and reacts with isocyanate through hydroxyl, the reaction speed of the system is slow, the curing time needs several hours, and the actual drying time needs about one day. The polyurea spraying material is generated by the reaction of an isocyanate component and an amino compound component, generally, isocyanate and amino-terminated polyether are adopted for reaction, the curing speed of the system is high, the mechanical property of a coating film is good, but the gel time is only a few seconds, the construction requirement is high, and the adhesion force between the formed coating and a base layer is poor, so that secondary recoating cannot be carried out.

Therefore, there is a need to develop a new pipeline spray repair material to overcome the above technical problems in the prior art.

Disclosure of Invention

It is a first object of the present invention to provide a polyurea resin composition that overcomes at least one of the above-mentioned deficiencies of the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a polyurea resin composition comprises the following components in parts by weight:

the component A comprises: 40-70 parts of isocyanate, 30-60 parts of pigment and filler and 1-5 parts of auxiliary agent I;

the component B comprises: 20-40 parts of organic amine curing agent, 60-80 parts of pigment and filler and 0-5 parts of auxiliary agent II;

when in use, the component A and the component B are mixed according to the volume ratio of 1-1.3: 1;

the organic amine curing agent is obtained by carrying out Michael addition reaction on a monomer containing a primary amine group and an olefin monomer containing a double bond.

According to the invention, the isocyanate is selected from one or more of dimers or trimers of aliphatic isocyanates and derivatives of dimers or trimers of aliphatic isocyanates.

According to the invention, the monomer containing primary amine groups is one or a mixture of two of methyl pentanediamine, isophorone diamine, ethylene diamine, hexamethylene diamine, 1,3 propane diamine, cyclohexane diamine, diethylene triamine and triethylene tetramine.

Preferably, the monomer containing primary amine groups is selected from one or a mixture of several of methyl pentanediamine, isophorone diamine, 1,3 propane diamine and cyclohexane diamine.

According to the invention, the olefin monomer containing double bonds is selected from one or a mixture of methyl acrylate, methyl methacrylate, butyl acrylate, diethyl maleate, dimethyl maleate, vinyl acetate, styrene and acrylonitrile.

Preferably one or a mixture of diethyl maleate, dimethyl maleate, vinyl acetate, styrene and acrylonitrile.

According to the invention, the molar ratio of the double bond-containing olefinic monomers to the primary amine group-containing monomers is 1-2: 1. Preferably 1.5-2: 1.

According to the invention, at least one of the auxiliary agent I and the auxiliary agent II comprises an anti-settling agent. The anti-settling agent is commonly used in epoxy spraying materials, polyurethane spraying materials and polyurea spraying materials, such as Degussa R972.

According to the invention, at least one of the auxiliary agent I and the auxiliary agent II comprises an adsorbent capable of adsorbing trace moisture, wherein the adsorbent is commonly used in epoxy spraying materials, polyurethane spraying materials and polyurea spraying materials, such as: molecular sieves such as griiss A3 and 4A molecular sieves.

According to the invention, the pigment and filler are pigment and filler commonly used in the existing epoxy spraying material, polyurethane spraying material and polyurea spraying material, such as: silicon dioxide, titanium dioxide, calcium carbonate, magnesium carbonate.

According to the invention, the preparation method of the organic amine curing agent comprises the following steps:

a) adding a monomer containing primary amine groups into a reaction container, and starting stirring;

b) slowly dripping an olefin monomer containing double bonds, controlling the dripping temperature to be 20-60 ℃, and the dripping time to be 2-4 h; the molar ratio of the olefin monomer containing double bonds to the monomer of primary amine groups is 1-2:1, and a mixed material is obtained;

c) heating the mixed material obtained in the step b), and carrying out Michael addition reaction at the reaction temperature of 60-90 ℃ for 3-8h to obtain a reaction material;

d) removing the unreacted monomers from the reaction materials in the step c) under the vacuum condition to obtain the organic amine curing agent.

In the step d), the vacuum condition is preferably (-0.095MPa) - (-0.090MPa)

The second object of the present invention is to provide a method for preparing the polyurea resin composition, comprising the steps of:

(1) preparing a component A: putting the isocyanate, the pigment filler and the auxiliary agent I in a formula ratio into a clean closed kettle, stirring and mixing at a high speed under the protection of nitrogen until the mixture is uniformly stirred, discharging and sealing for later use;

(2) preparing a component B: putting the organic amine curing agent, the pigment and filler and the auxiliary agent II in a formula ratio into a clean closed kettle, stirring and mixing at a high speed under the protection of nitrogen until the mixture is uniformly stirred, discharging and sealing for later use;

when in use, the component A and the component B are mixed according to the volume ratio of 1-1.3: 1.

The third object of the present invention is to provide a method for constructing the polyurea resin composition, comprising the steps of:

(1) respectively heating the component A and the component B to 40-60 ℃;

(2) and mixing the component A and the component B in a volume ratio of 1-1.3:1 by adopting double-pipe airless spraying equipment to form a liquid mixture, spraying and coating the liquid mixture on the inner wall of the pipeline to form the polyurea coating material.

Compared with the prior art, the invention has the following beneficial technical effects:

1) the polyurea resin composition has good adhesive force with a base layer, and can be sprayed for the second time, so the polyurea resin composition has wide application in pipeline repairing spraying or other aspects.

2) The polyurea resin composition is suitable for high-pressure spraying or airless spraying, is insensitive to humidity, and can be continuously sprayed, so that a continuous and integrated lining repairing material is formed on the inner wall of a pipeline.

3) The polyurea resin composition disclosed by the invention does not contain a solvent, and is safe and environment-friendly.

Detailed Description

The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.

In the following examples, the monomers containing primary amine groups are selected from:

methylpentamethylenediamine (abbreviated as PD code), isophoronediamine (abbreviated as IPD code), diethyl maleate (abbreviated as DEM code), acrylonitrile (abbreviated as AN code).

In the following examples, Colesine N100(N100 isocyanate) is a dimer of aliphatic isocyanate, Colesine 3600(N3600 isocyanate) and HK isocyanate of Tosoh chemical are trimers of aliphatic isocyanate, and the free isocyanate monomer of the trimer of aliphatic isocyanate is less than 1% by weight.

Adsorbent: grace A3, a commercial product

Anti-settling agent: degussa R972, commercially available product

In the comparative example, the polyetheramine used was Jeffamine D400 by Henschel.

Preparation example 1 preparation of organic amine curing agent D1

a) 85g of methyl pentanediamine monomer is added into the reaction vessel, and the stirring is started.

b) Slowly dropping 123g of methyl acrylate monomer into the reaction container, controlling the dropping time to be 3 hours, controlling the dropping temperature to be 40 ℃, and obtaining a mixed material after the dropping is finished;

c) and c), heating the mixed material obtained in the step b) to 75 ℃ to carry out Michael addition reaction, and controlling the reaction time to be 4 hours to obtain a reaction material.

d) And removing the unreacted monomers from the reaction material obtained in the step c) under the vacuum condition with the pressure of-0.095 MPa to obtain the organic amine curing agent D1. The general performance of test D1 is shown in table 1.

The molar ratio of the olefinic monomers containing double bonds and the monomers containing primary amine groups in this preparation example was calculated to be 1.96: 1.

Preparation example 2 preparation of organic amine curing agent D2

a) 85g of methyl pentanediamine monomer is added into the reaction vessel, and the stirring is started.

b) Slowly dropwise adding 86g of methyl acrylate monomer and 67g of diethyl maleate monomer into a reaction container, controlling the dropwise adding time to be 3.5 hours, controlling the dropwise adding temperature to be 45 ℃, and obtaining a mixed material after the dropwise adding is finished;

c) and c), heating the mixed material obtained in the step b) to 73 ℃ to perform Michael addition reaction, and controlling the reaction time to be 6 hours to obtain a reaction material.

d) And removing the unreacted monomers from the reaction material obtained in the step c) under the vacuum condition with the pressure of-0.095 MPa to obtain the organic amine curing agent D2. The general performance of test D2 is shown in table 1.

The molar ratio of the olefinic monomers containing double bonds to the monomers containing primary amine groups in this preparation example was calculated to be 2: 1.

Preparation example 3 preparation of organic amine curing agent D3

a) 58g of diethylenetriamine monomer is added into the reaction vessel, and stirring is started.

b) Slowly dropwise adding 169g of diethyl maleate monomer into a reaction container, controlling the dropwise adding time to be 3 hours, controlling the dropwise adding temperature to be 30 ℃, and obtaining a mixed material after the dropwise adding is finished;

c) and c), heating the mixed material obtained in the step b) to 80 ℃ to carry out Michael addition reaction, and controlling the reaction time to be 5 hours to obtain a reaction material.

d) And removing the unreacted monomers from the reaction material obtained in the step c) under the vacuum condition with the pressure of-0.095 MPa to obtain the organic amine curing agent D3. The general performance of test D3 is shown in table 1.

The molar ratio of olefinic monomers containing double bonds and monomers containing primary amine groups in this preparation example was calculated to be 1.75: 1.

Preparation example 4 preparation of organic amine curing agent D4

a) 38g of diethylenetriamine and 23g of methylpentamethylenediamine monomer are added into a reaction vessel, and stirring is started.

b) Slowly dripping 156g of dimethyl maleate monomer into the reaction container, controlling the dripping time to be 3 hours, controlling the dripping temperature to be 50 ℃, and obtaining a mixed material after finishing dripping;

c) and c), heating the mixed material obtained in the step b) to 80 ℃ to carry out Michael addition reaction, and controlling the reaction time to be 5 hours to obtain a reaction material.

d) And c) removing the unreacted monomers from the reaction mass obtained in the step c) under the vacuum condition of the pressure of-0.090 MPa to obtain the organic amine curing agent D4. The general performance of test D4 is shown in table 1.

The molar ratio of the olefinic monomers containing double bonds and the monomers containing primary amine groups in this preparation example was calculated to be 1.77: 1.

Preparation example 5 preparation of organic amine curing agent D5

a) 58g of diethylenetriamine monomer is added into the reaction vessel, and stirring is started.

b) Slowly dripping 122g of dimethyl maleate monomer into a reaction container, controlling the dripping time to be 3 hours, controlling the dripping temperature to be 30 ℃, and obtaining a mixed material after finishing dripping;

c) and c), heating the mixed material obtained in the step b) to 80 ℃ to carry out Michael addition reaction, and controlling the reaction time to be 5 hours to obtain a reaction material.

d) And removing the unreacted monomers from the reaction material obtained in the step c) under the vacuum condition with the pressure of-0.095 MPa to obtain the organic amine curing agent D5. The general performance of test D5 is shown in table 1.

The molar ratio of the olefinic monomers containing double bonds and the monomers containing primary amine groups in this preparation example was calculated to be 1.5: 1.

Preparation example 6 preparation of organic amine curing agent D6

a) 89g of isophorone diamine monomer was added to the reaction vessel and the stirring was turned on.

b) Slowly dripping 180g of diethyl maleate monomer into a reaction container, controlling the dripping time to be 4 hours, and the dripping temperature to be 60 ℃, and obtaining a mixed material after finishing dripping;

c) and c), heating the mixed material obtained in the step b) to 60 ℃ to carry out Michael addition reaction, and controlling the reaction time to be 4 hours to obtain a reaction material.

d) And removing the unreacted monomers from the reaction material obtained in the step c) under the vacuum condition with the pressure of-0.095 MPa to obtain the organic amine curing agent D6. The general performance of test D6 is shown in table 1.

The molar ratio of the olefinic monomers containing double bonds to the monomers containing primary amine groups in this preparation example was calculated to be 2: 1.

Preparation example 7 preparation of organic amine curing agent D7

a) 89g of isophorone diamine monomer was added to the reaction vessel and the stirring was turned on.

b) Slowly dripping 53g of acrylonitrile monomer into the reaction container, controlling the dripping time to be 2 hours, and the dripping temperature to be 40 ℃, and obtaining a mixed material after finishing dripping;

c) and c), heating the mixed material obtained in the step b) to 80 ℃ to carry out Michael addition reaction, and controlling the reaction time to be 4 hours to obtain a reaction material.

d) And removing the unreacted monomers from the reaction material obtained in the step c) under the vacuum condition with the pressure of-0.095 MPa to obtain the organic amine curing agent D7. The conventional performance of the test with D7 is shown in table 1.

The molar ratio of the olefinic monomers containing double bonds and the monomers containing primary amine groups in this preparation example was calculated to be 1.91: 1.

Preparation example 8 preparation of organic amine curing agent 7

a) 74.14g of 1, 3-propanediamine monomer was added to the reaction vessel and the stirring was turned on.

b) Slowly dripping 129.14g of vinyl acetate monomer into the reaction container, controlling the dripping time to be 2 hours, and the dripping temperature to be 20 ℃, and obtaining a mixed material after finishing dripping;

c) and c), heating the mixed material obtained in the step b) to 90 ℃ to carry out Michael addition reaction, and controlling the reaction time to be 4 hours to obtain a reaction material.

d) And c) removing the unreacted monomers from the reaction mass obtained in the step c) under the vacuum condition of the pressure of-0.090 MPa to obtain the organic amine curing agent D8. The conventional performance of the test with D8 is shown in table 1.

The molar ratio of the olefinic monomers containing double bonds and the monomers containing primary amine groups in this preparation example was calculated to be 1.5: 1.

TABLE 1 general Properties of organic amine curing agents D1-D8

EXAMPLES 1-8 preparation of polyurea resin compositions

The polyurea resin composition formulation is shown in table 2.

TABLE 2 polyurea resin composition formulations

A method for preparing a polyurea resin composition, comprising the steps of:

(1) preparing a component A: putting the isocyanate, the pigment filler and the auxiliary agent I in a formula ratio into a clean closed kettle, stirring and mixing at a high speed under the protection of nitrogen until the mixture is uniformly stirred, discharging and sealing for later use;

(2) preparing a component B: putting the organic amine curing agent, the pigment and filler and the auxiliary agent II in a formula ratio into a clean closed kettle, stirring and mixing at a high speed under the protection of nitrogen until the mixture is uniformly stirred, discharging and sealing for later use;

polyurea resin compositions E1 to E8 were prepared according to the above preparation methods according to formulations 1 to 8, and were ready for use.

Comparative example 1

Polyurea resin composition E9 was prepared according to the above preparation method according to the formulation of comparative example 1 and was ready for use.

Performance test of polyurea resin compositions E1-E8 of example 9 and polyurea resin composition E9 of comparative example 1

The polyurea resin compositions prepared in examples 1 to 8 and the polyurea resin composition of comparative example 1 were heated to 40 to 60 ℃ respectively for component A and component B, and then the component A and the component B were mixed in a volume ratio of 1:1 by a twin-tube airless spray apparatus to form a liquid mixture, which was sprayed and coated on the inner wall of a pipe to form a polyurea coating material, and various properties of the polyurea coating were examined as shown in Table 3.

TABLE 3 comparison of the properties of the polyurea resin compositions E1-E8 and the polyurea resin composition E9 of comparative example 1

As can be seen from the data in Table 3, the polyurea resin compositions prepared in examples 1 to 8 have gel times of 12 to 18 seconds after being sprayed on the inner surface of the pipe, which are slower than those of comparative example 1, but much faster than those of the polyurethane spray material. The tack-free time was 40-56 seconds, slower than comparative example 1, but much faster than the polyurethane spray. As can be seen, the polyurea resin compositions prepared in examples 1-8 gel quickly, but not so quickly as to ensure sustainable spray application.

The polyurea resin compositions prepared in examples 1 to 8 have good tensile strength and adhesive strength after being sprayed on the inner surface of the pipeline, and the tensile strength and the adhesive strength are both obviously greater than those of comparative example 1, namely, the polyurea resin compositions prepared in examples 1 to 8 have good adhesion with the base layer, and good recoatability, and can be sprayed for the second time, thus being widely applied to pipeline repairing spraying or other aspects.

Meanwhile, the polyurea resin composition prepared in the embodiments 1 to 8 is suitable for high-pressure spraying or airless spraying, is not sensitive to humidity, and can be continuously sprayed, so that a continuous and integrated lining repairing material is formed on the inner wall of a pipeline, and the composition does not contain a solvent, is safe and environment-friendly, and can be used as a trenchless pipeline repairing material.

The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications or alterations to this practice will occur to those skilled in the art and are intended to be within the scope of this invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (8)

1. The polyurea resin composition is characterized by comprising the following components in parts by weight:

the component A comprises: 40-70 parts of isocyanate, 30-60 parts of pigment and filler and 1-5 parts of auxiliary agent I;

the component B comprises: 20-40 parts of organic amine curing agent, 60-80 parts of pigment and filler and 0-5 parts of auxiliary agent II;

when in use, the component A and the component B are mixed according to the volume ratio of 1-1.3: 1;

the organic amine curing agent is obtained by carrying out Michael addition reaction on a monomer containing a primary amine group and an olefin monomer containing a double bond;

the monomer containing primary amine groups is one or a mixture of several of methyl pentanediamine, isophorone diamine, ethylene diamine, hexamethylene diamine, 1, 3-propane diamine, cyclohexane diamine, diethylene triamine and triethylene tetramine;

at least one of the auxiliary agent I and the auxiliary agent II comprises an anti-settling agent;

at least one of the auxiliary agent I and the auxiliary agent II comprises an adsorbent capable of adsorbing trace moisture;

the olefin monomer containing double bonds is selected from one or a mixture of methyl acrylate, methyl methacrylate, butyl acrylate, vinyl acetate, styrene and acrylonitrile.

2. The polyurea resin composition according to claim 1, wherein the olefin monomer containing double bonds is selected from one or more of methyl acrylate, vinyl acetate, and acrylonitrile.

3. The polyurea resin composition of claim 1, wherein the isocyanate is selected from one or more of a dimer or trimer of an aliphatic isocyanate and a derivative of the dimer or trimer of an aliphatic isocyanate.

4. The polyurea resin composition according to claim 1, wherein: the monomer containing primary amine groups is one or a mixture of several of methyl pentanediamine, isophorone diamine, 1, 3-propane diamine and diethylenetriamine.

5. The polyurea resin composition according to claim 1, wherein: the molar ratio of the olefin monomer containing double bonds to the monomer containing primary amine groups is 1-2: 1.

6. The polyurea resin composition of claim 1, wherein the molar ratio of the double bond-containing olefinic monomer to the primary amine group-containing monomer is 1.5 to 2: 1.

7. A method for preparing the polyurea resin composition of any one of claims 1 to 6, comprising the steps of:

(1) preparing a component A: putting the isocyanate, the pigment filler and the auxiliary agent I in a formula ratio into a clean closed kettle, stirring and mixing at a high speed under the protection of nitrogen until the mixture is uniformly stirred, discharging and sealing for later use;

(2) preparing a component B: putting the organic amine curing agent, the pigment and filler and the auxiliary agent II in a formula ratio into a clean closed kettle, stirring and mixing at a high speed under the protection of nitrogen until the mixture is uniformly stirred, discharging and sealing for later use;

when in use, the component A and the component B are mixed according to the volume ratio of 1-1.3: 1.

8. A method of constructing the polyurea resin composition according to any one of claims 1 to 6, comprising the steps of:

(1) respectively heating the component A and the component B to 40-60 ℃;

(2) and mixing the component A and the component B in a volume ratio of 1-1.3:1 by adopting double-pipe airless spraying equipment to form a liquid mixture, spraying and coating the liquid mixture on the inner wall of the pipeline to form the polyurea coating material.