CN114015004B - Shock-absorbing polyurea rigid foam material and preparation method and application thereof - Google Patents
Shock-absorbing polyurea rigid foam material and preparation method and application thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08J2203/00—Foams characterized by the expanding agent
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention provides a shock-absorption polyurea rigid foam material and a preparation method and application thereof, wherein the preparation raw materials of the shock-absorption polyurea rigid foam material comprise a component A and a component B, and the preparation raw materials of the component A comprise the following components in parts by weight: 45-65 parts of polyether amine; 15-20 parts of 4,4' -bis-sec-butylaminodiphenylmethane; 3-10 parts of a physical foaming agent; 20-40 parts of an auxiliary agent; the B component comprises polymethylene polyphenyl isocyanate. The polyurea rigid foam material has a closed-cell structure, has excellent dynamic shear modulus while meeting the requirements of leakage prevention, heat preservation and heat insulation, can effectively prolong the service life of a damping layer, avoids lining cracking, and is suitable for running or building tunnels.
Description
Technical Field
The invention belongs to the technical field of tunnel operation and maintenance, and relates to a shock-absorbing polyurea rigid foam material, and a preparation method and application thereof.
Background
China is a mountainous country, and about 75% of the land is mountainous or heavily hilled. The tunnel engineering, as an important structure type, can shorten road mileage, ensure optimal alignment, improve technical standards, facilitate driving, effectively prevent severe weather and unfavorable geological disasters, improve driving safety, and simultaneously can be well coordinated with the local environment to preserve natural landscapes, thereby being widely applied. After the tunnel is built, various diseases occur in the long-term operation process, and diseases mainly comprise water damage, freeze damage, high geothermal heat damage, broken lining and the like.
The tunnel and the underground structure are provided with the damping layer, a certain material is arranged between the surrounding rock and the tunnel lining structure or the mechanical property of the surrounding rock in a certain range outside the lining is changed, and the rigidity of the material is properly adjusted, so that the aim of reducing the dynamic response of the tunnel lining structure can be fulfilled.
The high polymer material has the characteristics of light weight, quick reaction, good durability, excellent seepage-proofing performance and the like. Particularly, the spraying rigid foam is integrally formed to be used as the shock absorption layer, leakage points are eliminated theoretically, the unique closed-cell structure endows the shock absorption layer with the characteristics of excellent leakage prevention (water impermeability) and heat preservation and heat insulation, but the existing spraying rigid foam has the problem of insufficient durability, and the leakage condition occurs during the practical engineering application due to the influence of various dynamic stresses such as movement of soil strata and various vibrations after construction for a period of time, particularly after the leakage in winter and the freezing damage of northern alpine regions even can cause the cracking loss of linings.
The dynamic shear modulus can reflect the dynamic characteristics of the soft soil to a certain extent, is one of key parameters of the dynamic characteristics of the soil body, and has important functions in seismic research and engineering seismic resistance. The dynamic shear modulus is responsive to the deformation resistance of the material under dynamic stress, the greater the value, the greater the deformation resistance of the material. The dynamic shear modulus of the rigid foam materials in the prior art cannot meet the requirements of the shock-absorbing layer for the tunnel.
CN104119498A discloses flame-retardant polyurethane spraying rigid foam plastic, belonging to the field of rigid foam plastic. The rigid foam is prepared by polymerizing an isocyanate component and a polyol component according to the volume ratio of 1: 1; wherein the polyol component comprises polyester polyol, a reactive flame retardant, inorganic particles and an auxiliary agent, and the four components respectively account for 10-40%, 5-40%, 10-20% and 24-50% of the total weight of the polyol component. The flame-retardant polyurethane coating can be formed by spraying with a polyurethane high-pressure sprayer, and has excellent flame-retardant property. However, the properties of the polyurethane spray rigid foam plastic cannot meet the requirements of materials for tunnels.
Therefore, in the field, it is desired to develop a shock-absorbing polyurea rigid foam material which has excellent dynamic shear modulus while satisfying anti-leakage, heat preservation and insulation, and provides a new scheme for tunnel construction safety, operation durability and the like under complex geological conditions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a shock-absorbing polyurea rigid foam material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a shock-absorption polyurea rigid foam material, which comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
the B component comprises polymethylene polyphenyl isocyanate, preferably WANNATE2408, having a functionality of 3 and a viscosity of 400cps at 25 deg.C.
In the invention, the component A is a main agent, and the component B is a curing agent.
According to the invention, polyether amine in the component A reacts with the curing agent of the component B to obtain the polyurea rigid foam. Compared with carbamate (polyurethane), the hydrogen bond acting force in the carbamido group is much stronger, the intermolecular (i.e. interchain) interacting force in the polyurea structure is much stronger, the phase separation of hard chains such as the carbamido group and the polyisocyanurate group and the like and soft chains such as the polyether amine and the like is more obvious, the melting temperature of the hard chain section area of the polymer is higher than that of the polyurethane structure, compared with the performance of the elastomer product, the physical performance of the polyurea structure is far better than that of the polyurethane structure, the national standard requirement of the II type polyurea is that the tensile strength is more than or equal to 16MPa, the elongation at break is more than or equal to 450 percent, and the II type polyurea is a strong and tough elastomer material. However, polyurea has been used only as a waterproof coating or an elastomer or a soft open-cell foam, and cannot be used as a thermal insulation foam, because the pore wall of the foam cell has higher compressive strength to achieve a closed cell structure, and the physical foaming agent with a closed cell structure and a good thermal insulation effect can provide a lower thermal conductivity coefficient. To solve this problem, the present invention uses curing agent polymethylene polyphenyl isocyanate WANNATE2408 with functionality of 3, which not only can provide high crosslinking density to give higher compressive strength to the cell walls to obtain a closed cell structure, but also can trimerize to form polyisocyanurate hard segments by reacting with excess isocyanate group, and is an important component of the hard segments in the polyurea hard foam, and directly influences the dynamic shear modulus of the polyurea hard foam.
In the present invention, in the raw material for preparing the component a, the polyether amine may be used in an amount of 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, or the like.
In the invention, the amount of the 4,4' -bis-sec-butylaminodiphenylmethane in the raw material for preparing the component A can be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts.
In the present invention, the amount of the physical foaming agent used in the preparation raw material of the a component may be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or the like.
In the invention, the amount of the auxiliary agent in the raw materials for preparing the component A can be 20 parts, 25 parts, 30 parts, 35 parts or 40 parts.
Preferably, the volume ratio of the A component to the B component is 1: 1.
Preferably, the polyetheramine comprises T403 and/or D400, preferably T403 and D400. Wherein T403 is polyetheramine with functionality of 3 and molecular weight of 400, and D400 is polyetheramine with functionality of 2 and molecular weight of 400.
Preferably, the T403 is 25 to 35 parts by weight, such as 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, etc., and the D400 is 20 to 30 parts by weight, such as 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, etc.
In the main component of the invention, the weight ratio range of the T403, D400, 4' -bis-sec-butylaminodiphenylmethane and 3 raw materials participating in the reaction is as follows: (25-35) to (20-30): (15-20); the equivalent weight (molecular weight/functionality) is 133, 200 and 155 respectively, the smaller equivalent weight obtains more carbamido group hard segments, the mechanical property of the polyurea depends on the proportion of the soft/hard segments and the microphase separation degree of the soft/hard segments to a great extent, and the polyurea hard foam has higher compressive strength (more than or equal to 0.1MPa) by matching with the WANNATE2408 with 3 functionality in the curing agent.
Meanwhile, the improvement of the hard segment content in the main agent system is beneficial to improving the hard segment aggregation degree and the ordering degree thereof, the proportion weight of the curing agent in the raw material system is kept unchanged, and when the ratio of the hard segment to the hard segment is T403: when the weight ratio range of (D400+4,4' -bis-sec-butylaminodiphenylmethane) is less than 25: 50, the soft segment is a continuous phase, and hard segment particles are unevenly dispersed in the soft segment and are fewer in number; when the T403: when the weight ratio of (D400+4,4' -bis-sec-butylaminodiphenylmethane) is more than 35: 35, the hard segments are in a net-shaped crossed continuous phase, and the soft segments are instead converted into a dispersed phase to be dispersed in the hard segment network. This indicates that as the content of the hard segment increases, the hard segments are present in a more compact granular distribution, the hard segments gradually change from the dispersed phase to the continuous phase, and the soft segments gradually change from the continuous phase to the dispersed phase. When the T403: when the weight ratio of (D400+4,4' -bis-sec-butylaminodiphenylmethane) is in the range of (25-35) to (35-50), the soft segment is still continuous phase, but the uniform distribution degree of hard segment particles in the soft segment is increased, and the quantity is obviously increased, and the material has reasonable microphase separation degree and hard segment micro-region size, so that the material has better dynamic shear modulus.
Preferably, the physical blowing agent comprises a chlorofluorocarbon blowing agent, preferably HCFC-22.
Preferably, the adjuvant comprises a flame retardant and a surfactant.
Preferably, the auxiliary agent further comprises any one or a combination of at least two of a catalyst, water or color paste.
Preferably, the flame retardant is 85% to 98% (e.g., 85%, 88%, 90%, 93%, 95%, 98%, etc.), the surfactant is 2% to 6% (e.g., 2%, 3%, 4%, 5%, 6%, etc.), the catalyst is 0% to 3% (e.g., 0.5%, 1%, 2%, 3%, etc.), the water is 0% to 1% (e.g., 0.5%, 1%, etc.), and the color paste is 0% to 5% (e.g., 0.5%, 1%, 2%, 3%, 4%, 5%, etc.), based on 100% by weight of the additive.
Preferably, the flame retardant comprises tris (2-chloroethyl) phosphate and/or diethyl ethylphosphate. In the present invention, the flame retardant also functions to reduce viscosity and also acts as a viscosity reducer.
Preferably, the surfactant comprises polydimethylsiloxane, preferably DC193 (dow corning).
Preferably, the catalyst comprises an amine catalyst, preferably any one of dimethylcyclohexylamine, triethylenediamine, pentamethyldiethyltriamine or a quaternary ammonium salt or a combination of at least two thereof.
Preferably, the color paste comprises any one of 126-3M1665, 036-2M1941, P89855, P89750 and P89856.
Another problem solved by the present invention is the foaming expansion of polyurea rigid foams. Because the reaction speed of the polyether amine and the curing agent isocyanate is very high, and compared with water, the reaction speed of the polyether amine and the curing agent isocyanate is about 1000 times faster, the chemical foaming agent water in a system is not ready to react with the isocyanate to release carbon dioxide gas, the physical foaming agent chlorofluorocarbon is not ready to be sufficiently gasified to obtain uniform foam, and the reaction of the polyether amine and the curing agent isocyanate is finished, so that an ideal foam structure cannot be obtained.
The idea of the invention for solving the problem is to introduce 15-20 parts of 4,4' -bis-sec-butylaminodiphenylmethane into the polyurea rigid foam main agent and simultaneously use a chlorofluorocarbon physical foaming agent with the boiling point lower than the lowest construction temperature (0 ℃) of concrete under the standard atmospheric pressure.
4,4' -bis-sec-butylaminodiphenylmethane is a liquid secondary diamine in which the hydrogen atom on each amino group is replaced by a sec-butyl group, the combination of the active hydrogen atom and the sec-butyl group in a confined space gives rise to a number of unique properties, the amino moiety forming a urea linkage which affects the hard segment, and the butyl group acting as an internal plasticizer. Because of the large spatial position near the secondary diamine of the reactive group, the gel reaction speed of the polyurea can be greatly reduced, and the prolonged gel speed can improve the adhesiveness and the fluidity with the base layer, the combination between the coating and the surface quality. More importantly, the modified isocyanate is used as a main reaction raw material, and the prolonged gel speed is time for the reaction of a chemical foaming agent in the system and isocyanate to release carbon dioxide gas. Meanwhile, the chlorofluorocarbon physical foaming agent with the boiling point lower than the lowest construction temperature (0 ℃) of concrete under the standard atmospheric pressure is used, the reaction heat gasification of the main agent and the curing agent is not needed to be changed into foaming gas, the foaming gas can be instantly gasified when entering a spray gun mixing chamber through a high-pressure pipeline, and the mixed liquid of the main agent and the curing agent forms uniform liquid foam in the spray gun mixing chamber and is then sprayed out.
The invention solves the last problem that the main agent cannot be stored and used at normal temperature and normal pressure due to the gasification of the foaming agent after containing the chlorofluorocarbon physical foaming agent with the boiling point lower than the minimum construction temperature (0 ℃) of concrete under the standard atmospheric pressure. The physical foaming agent has the following characteristics: the boiling point of the chlorofluorocarbon foaming agent under the standard atmospheric pressure is lower than the minimum construction temperature (0 ℃) of concrete, the chlorofluorocarbon foaming agent is non-combustible, and the vapor pressure of the chlorofluorocarbon foaming agent after being dissolved in the main agent components according to a proportion is not more than about 0.5 standard atmospheric pressure.
Therefore, the invention compares the temperature-vapor pressure curve of the chlorofluorocarbon physical foaming agents such as HFC-227ea (boiling point-16.4 ℃), HFC-152a (boiling point-24.7 ℃), HFC-134a (boiling point-26.5 ℃) and HCFC-22 (boiling point-41 ℃) in a closed container according to the formula proportion, and finally, unexpectedly finds that HCFC-22 (boiling point-41 ℃) has the lowest boiling point and the highest vapor pressure in the monomer gas state, but has the lowest vapor pressure after being dissolved in the main agent, and the vapor pressure (20 ℃) is not more than 0.5 standard atmospheric pressure after being dissolved in the main agent component according to the proportion. The temperature-vapor pressure profile of HCFC-22 dissolved in the main component at 10% by weight in a closed container is shown in FIG. 1.
In a second aspect, the present invention provides a method for preparing the rigid foam material of shock-absorbing polyurea according to the first aspect, comprising the following steps:
(1) mixing the polyether amine, the 4,4' -bis-sec-butylaminodiphenylmethane, the physical foaming agent and the auxiliary agent according to the formula ratio to obtain a component A;
(2) and mixing the component A and the component B, and spraying to obtain the shock-absorbing polyurea rigid foam material.
Preferably, the temperature of the mixing is 50-60 ℃, such as 50 ℃, 53 ℃, 55 ℃, 58 ℃ or 60 ℃ and the like.
In the actual construction process, a polyurethane high-pressure sprayer is used for mixing and uniformly spraying A, B two components on working surfaces such as tunnel inner walls and the like needing damping layers, and the method specifically comprises the following steps:
(1) mixing the polyether amine, the 4,4' -bis-sec-butylaminodiphenylmethane, the physical foaming agent and the auxiliary agent according to the formula ratio to obtain a component A;
(2) respectively inserting two groups of material extracting pumps of a spraying machine into a group A raw material barrel and a group B raw material barrel, turning on a power supply and an air compressor, setting the heating temperature of the raw materials of the spraying machine and pipelines to be 55 ℃, spraying the mixed raw materials on a base material by using a spray gun, and spraying more than 5 layers to obtain the damping polyurea rigid foam material with the thickness of 5-10 cm.
In a third aspect, the present invention provides the use of the rigid foam material of vibration damping polyurea described in the first aspect in tunnel engineering.
Compared with the prior art, the invention at least has the following beneficial effects:
the invention controls the contents of the polyetheramine and the 4,4' -bis-sec-butylaminodiphenylmethane within a certain range, and simultaneously is matched with the high-functionality polymethylene polyphenyl isocyanate WANNATE2408 for use, so that the prepared shock absorption polyurea rigid foam has higher heat preservation effect (compressive strength) and dynamic shear modulus. In addition, the invention solves the problem of foaming expansion of the polyurea material by the synergistic use of the 4,4' -bis-sec-butyl amino diphenylmethane and the physical foaming agent. The shock-absorbing polyurea hard foam material has the characteristics of closed cell structure (the closed cell rate is more than or equal to 90 percent), impermeability, heat conductivity coefficient of less than or equal to 0.028W/(m.k) (23 ℃) and compressive strength of more than or equal to 0.1MPa, and the highest dynamic shear modulus can reach 100 MPa.
Drawings
Figure 1 is a graph of temperature versus vapor pressure of HCFC-22 in a closed container after dissolution of the host component.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw materials and the grades used in the examples and comparative examples of the invention are shown in the following table:
example 1
In this embodiment, a rigid foam material of shock absorption polyurea is provided, and the raw materials for preparing the rigid foam material of shock absorption polyurea comprise a component a and a component B, and the raw materials for preparing the component a comprise the following components in parts by weight:
the B component is polymethylene polyphenyl isocyanate (WANNATE 2408).
Wherein the volume ratio of the component A to the component B is 1: 1; the grade of the 4,4' -bis-sec-butylaminodiphenylmethane is WanaLink 6200; the physical foaming agent is HCFC-22; the flame retardant is TCPP (Ten thousand flourishing); the surfactant is polydimethylsiloxane DC193 (dow corning); the catalyst is dimethyl cyclohexylamine; the water is tap water; the color paste is 036-2M 1941.
The preparation method comprises the following steps:
(1) mixing the polyether amine, the 4,4' -di-sec-butyl amino diphenylmethane, the physical foaming agent and various auxiliaries according to the formula ratio to obtain a component A;
(2) respectively inserting two groups of material lifting pumps of a spraying machine into a group A raw material barrel and a group B raw material barrel, turning on a power supply and an air compressor, setting the heating temperature of the raw materials of the spraying machine and a pipeline to be 55 ℃, spraying the mixed raw materials on a base material by using a spray gun, and spraying more than 5 layers to obtain the shock-absorbing polyurea hard foam material with the thickness of 10 cm.
Example 2
In this embodiment, a rigid foam material of shock absorption polyurea is provided, and the raw materials for preparing the rigid foam material of shock absorption polyurea comprise a component a and a component B, and the raw materials for preparing the component a comprise the following components in parts by weight:
the B component is polymethylene polyphenyl isocyanate (WANNATE 2408).
Wherein the volume ratio of the component A to the component B is 1: 1; the physical foaming agent is HCFC-22; the flame retardant is TCPP (Ten thousand flourishing); the surfactant is polydimethylsiloxane DC193 (dow corning); the water is tap water; the color paste is 036-2M 1941.
The preparation method comprises the following steps:
(1) mixing the polyether amine, the 4,4' -di-sec-butyl amino diphenylmethane, the physical foaming agent and various auxiliaries according to the formula ratio to obtain a component A;
(2) respectively inserting two groups of material lifting pumps of a spraying machine into a group A raw material barrel and a group B raw material barrel, turning on a power supply and an air compressor, setting the heating temperature of the raw materials of the spraying machine and a pipeline to be 55 ℃, spraying the mixed raw materials on a base material by using a spray gun, and spraying more than 5 layers to obtain the shock-absorbing polyurea hard foam material with the thickness of 10 cm.
Example 3
In this embodiment, a rigid foam material of shock absorption polyurea is provided, and the raw materials for preparing the rigid foam material of shock absorption polyurea comprise a component a and a component B, and the raw materials for preparing the component a comprise the following components in parts by weight:
the B component is polymethylene polyphenyl isocyanate (WANNATE 2408).
Wherein the volume ratio of the component A to the component B is 1: 1; the physical foaming agent is HCFC-22; the flame retardant is TCPP (Ten thousand flourishing); the surfactant is polydimethylsiloxane DC193 (dow corning); the catalyst is dimethyl cyclohexylamine; the water is tap water; the color paste is 036-2M 1941.
The preparation method comprises the following steps:
(1) mixing the polyether amine, the 4,4' -di-sec-butyl amino diphenylmethane, the physical foaming agent and various auxiliaries according to the formula ratio to obtain a component A;
(2) respectively inserting two groups of material lifting pumps of a spraying machine into a group A raw material barrel and a group B raw material barrel, turning on a power supply and an air compressor, setting the heating temperature of the raw materials of the spraying machine and a pipeline to be 55 ℃, spraying the mixed raw materials on a base material by using a spray gun, and spraying more than 5 layers to obtain the shock-absorbing polyurea hard foam material with the thickness of 10 cm.
Example 4
This example is different from example 1 only in that the weight part of polyetheramine T403 in the raw material is 55 parts, and polyetheramine D400 is not included, and the other conditions are the same as example 1.
Example 5
This example is different from example 1 only in that the weight part of polyetheramine D400 in the raw material for preparation is 55 parts, and polyetheramine T403 is not included, and the other conditions are the same as example 1.
Comparative example 1
This comparative example differs from example 1 only in that the three starting materials polyetheramine T403, polyetheramine D400 and 4,4' -bis-sec-butylaminodiphenylmethane in the preparation were replaced by the following starting materials, and the other conditions were the same as in example 1.
4035 parts of polyether polyol;
polyether polyol R4110b 30 parts;
PS 315235 parts of polyester polyol;
comparative example 1 a rigid polyurethane foam was obtained, which was different from the rigid polyurea foam of example 1, and a comparison was made between the properties of the rigid polyurea foam and the rigid polyurethane foam of similar densities.
Comparative example 2
This comparative example differs from example 2 only in that the three starting materials polyetheramine T403, polyetheramine D400 and 4,4' -bis-sec-butylaminodiphenylmethane in the preparation were replaced by the following starting materials, and the other conditions were the same as in example 2.
4035 parts of polyether polyol;
polyether polyol R4110b 33 parts;
PS 315235 parts of polyester polyol;
comparative example 2A rigid polyurethane foam was obtained by distinguishing it from the rigid polyurea foam of example 2, and a comparison was made between the properties of the rigid polyurea foam and the rigid polyurethane foam of similar densities.
Comparative example 3
This comparative example differs from example 3 only in that the three starting materials polyetheramine T403, polyetheramine D400 and 4,4' -bis-sec-butylaminodiphenylmethane in the preparation were replaced by the following starting materials, and the other conditions were the same as in example 3.
4035 parts of polyether polyol;
polyether polyol R4110b 34 parts;
PS 315235 parts of polyester polyol;
comparative example 3 a rigid polyurethane foam was obtained by distinguishing it from the rigid polyurea foam of example 3, and a comparison was made between the properties of a rigid polyurea foam and a rigid polyurethane foam of similar densities.
Comparative example 4
This comparative example differs from example 1 only in that 4,4' -bis-sec-butylaminodiphenylmethane was replaced with an equal amount of D400 and the other conditions were the same as in example 1.
Comparative example 5
This comparative example differs from example 1 only in that the polymethylene polyphenyl isocyanate (WANNATE 2408) is replaced by the same amount of isocyanate for polyurea WANEFOAM 8312 (Wawawa chemical), the other conditions being the same as in example 1.
The rigid foam materials of vibration damping polyurea of examples 1 to 5 and comparative examples 1 to 5 were subjected to a performance test by the following method:
(1) thermal conductivity (23 ℃): testing according to the method of GB/T3399;
(2) compressive strength: testing according to the method of GB/T8813;
(3) water permeability: testing was carried out according to the method of GB50404-2007 appendix A;
(4) dynamic shear modulus: carrying out a resonance column experiment on the shock absorption polyurea rigid foam material to obtain a damping ratio, and then carrying out a resonance column experiment according to a formula Gd＝(2πfnthc/βs)2ρ0×10-4Obtaining the dynamic shear modulus, wherein: gd-dynamic shear modulus (kPa); f. ofnt-the torsional resonance frequency (Hz) measured at the time of the test; beta is as-a torsional dimensionless frequency factor; ρ is a unit of a gradient0Density of the sample (g/cm)3)；
(5) Closed pore rate: the test was carried out according to the method of GB/T10799.
The results of the performance tests are shown in table 1.
TABLE 1
As can be seen from Table 1, in examples 1 to 3, as the density of the polyurea rigid foam material increases, the compressive strength (0.11 to 0.26MPa), the closed cell ratio (92 to 97 percent), and the dynamic shear modulus (30.19 to 100.16MPa) increase, but the heat insulating effect decreases (the thermal conductivity increases).
When T403 in the formulations of examples 1, 2, 3: when the weight ratio of (D400+4,4' -bis-sec-butylaminodiphenylmethane) is (25-35) to (35-50), the soft segment is still continuous phase, but the uniform distribution degree of hard segment particles in the soft segment is increased, and the quantity is obviously increased, so that the material has reasonable microphase separation degree and hard segment micro-area size, and has better dynamic shear modulus.
T403 in example 4: the weight ratio range of (D400+4,4' -bis-sec-butylaminodiphenylmethane) is more than 35: 35, the hard segment is in a net crossed continuous phase, and the soft segment is instead converted into a dispersed phase to be dispersed in the hard segment network. As the hard segment content increases, the hard segments are present in a more compact granular distribution, the compressive strength of the material increases, but the dynamic shear modulus decreases substantially.
T403 in example 5: the weight ratio range of (D400+4,4' -bis-sec-butylaminodiphenylmethane) is less than 25: 50, the soft segment is a continuous phase, and the hard segment particles are unevenly dispersed in the soft segment and are fewer in quantity; the compressive strength of the material is less than 0.1MPa (one atmosphere), the foam shrinks and cannot be tested.
Comparative examples 1, 2, 3 rigid polyurethane foams correspond to the rigid polyurea foams of examples 1, 2, 3, respectively, and comparisons were made of the properties of the rigid polyurea foams and the rigid polyurethane foams of similar densities. It can be seen that the compressive strength of the polyurethane rigid foam is increased more, the thermal conductivity and the closed cell rate are slightly increased, but the dynamic shear modulus is almost doubled. From these data, it can be clearly judged that the properties of the spray polyurea rigid foam material are superior to those of the spray polyurethane rigid foam material in the aspect of the dynamic characteristics of the high polymer material represented by the dynamic shear modulus, and the spray polyurea rigid foam material is more suitable for being applied to the seismic structure of the tunnel.
In comparative example 4, the polyether amine D400 is used instead of 4,4' -bis-sec-butylaminodiphenylmethane, because the reaction speed of the polyether amine and the curing agent isocyanate is very high, compared with water, the reaction speed of the polyether amine and the curing agent isocyanate is about 1000 times faster, the chemical foaming agent water in the system has not been available to react with the isocyanate to release carbon dioxide gas, the physical foaming agent chlorofluorocarbon has not been sufficiently gasified to obtain uniform foam, the reaction of the polyether amine and the curing agent isocyanate has been finished, and the sample sheet is in an irregular honeycomb shape and cannot be tested.
In comparative example 5, where the high functionality (functionality 3) WANEFOAM2408 was replaced with the equivalent amount of the isocyanate for polyurea WANEFOAM 8312 (functionality 2) (Wanhua chemistry), the compressive strength of the material was < 0.1MPa (one atmosphere) due to the low functionality of the system and insufficient crosslinking, the foam shrunk and could not be tested.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it is not intended that the present invention is necessarily dependent on the above examples for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (15)
1. The shock-absorption polyurea rigid foam material is characterized in that the preparation raw materials of the shock-absorption polyurea rigid foam material comprise a component A and a component B, and the preparation raw materials of the component A comprise the following components in parts by weight:
the polyetheramines include T403 and D400;
the weight portion of the T403 is 25-35 parts, and the weight portion of the D400 is 20-30 parts;
the B component comprises polymethylene polyphenyl isocyanate which is WANNATE 2408.
2. The rigid foam shock absorbing polyurea foam according to claim 1, wherein the volume ratio of the A component to the B component is 1: 1.
3. The rigid foam shock absorbing polyurea foam according to claim 1, wherein the physical blowing agent comprises a chlorofluorocarbon blowing agent.
4. The rigid foam shock absorbing polyurea foam according to claim 3, wherein the chlorofluorocarbon blowing agent is HCFC-22.
5. The rigid foam shock absorbing polyurea foam according to claim 1, wherein the auxiliary comprises a flame retardant and a surfactant.
6. The rigid foam material of shock-absorbing polyurea according to claim 5, wherein the auxiliary agent further comprises any one of a catalyst, water or a color paste or a combination of at least two of the above.
7. The shock-absorbing polyurea rigid foam material according to claim 6, wherein the content of the flame retardant is 85-98%, the content of the surfactant is 2-6%, the content of the catalyst is 0-3%, the content of the water is 0-1%, and the content of the color paste is 0-5%, based on 100% by weight of the additive.
8. The rigid foam shock absorbing polyurea foam according to claim 5, wherein the flame retardant comprises tris (2-chloroethyl) phosphate and/or diethyl ethylphosphate.
9. The rigid foam shock absorbing polyurea foam according to claim 5, wherein the surfactant comprises polydimethylsiloxane.
10. The rigid foam shock absorbing polyurea foam according to claim 6, wherein the catalyst comprises an amine catalyst.
11. The rigid foam material of claim 10, wherein the catalyst comprises any one of dimethylcyclohexylamine, triethylenediamine, pentamethyldiethyltriamine, or quaternary ammonium salts, or a combination of at least two thereof.
12. The shock absorbing polyurea rigid foam material of claim 6, wherein the color paste comprises any one of 126-3M1665, 036-2M1941, P89855, P89750, or P89856.
13. The method for preparing a shock absorbing polyurea rigid foam material according to any one of claims 1 to 12, wherein the method comprises the following steps:
(1) mixing the polyether amine, the 4,4' -bis-sec-butylaminodiphenylmethane, the physical foaming agent and the auxiliary agent according to the formula ratio to obtain a component A;
(2) and mixing the component A and the component B, and spraying to obtain the shock-absorbing polyurea rigid foam material.
14. The method of claim 13, wherein the temperature of the mixing is 50-60 ℃.
15. Use of a rigid foam shock-absorbing polyurea according to any one of claims 1 to 12 in tunnel engineering.
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