CN113683749A - High-overload-resistant light polyurea and preparation method thereof - Google Patents
High-overload-resistant light polyurea and preparation method thereof Download PDFInfo
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 39
- -1 amino compound Chemical class 0.000 claims abstract description 31
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000012530 fluid Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 150000004986 phenylenediamines Chemical group 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 229920000162 poly(ureaurethane) Polymers 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 23
- 239000003822 epoxy resin Substances 0.000 description 9
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- 239000011324 bead Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 239000004202 carbamide Substances 0.000 description 2
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- 230000002349 favourable effect Effects 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention belongs to the technical field of adhesives based on polyurea or polyurethane, and discloses a high overload resistant light polyurea and a preparation method thereof, wherein the high overload resistant light polyurea comprises an amino compound, a light filler and isocyanate, and the amino compound comprises a curing agent, a chain extender and an organic solvent; the preparation method of the high-overload-resistant light polyurea comprises the steps of fully mixing a chain extender, a curing agent and an organic solvent to form an amino compound; then adding the light filler into the amino compound component to form a blend; adding isocyanate into the blend to form a high viscosity fluid; and finally pouring the high-viscosity fluid into a mold, and standing at room temperature to obtain the high-overload-resistant light polyurea. The invention solves the problem that the use effect and the range of the low-density polyurea are limited due to the weak mechanical property of the low-density polyurea caused by the limitation of the internal structure of the existing polyurea.
Description
Technical Field
The invention belongs to the technical field of adhesives based on polyurea or polyurethane, and particularly relates to high-overload-resistant light polyurea and a preparation method thereof.
Background
Polyurea is a high molecular material and has the characteristics of wear resistance, water resistance, impact resistance, fatigue resistance, high temperature resistance, strong hydrophobicity and the like; the paint is insensitive to the environmental humidity, can completely isolate the moisture and oxygen in the air from permeating, and has excellent anti-corrosion performance; meanwhile, polyurea also has better rigidity and flexibility and excellent physical and mechanical properties, so that in recent years, polyurea is widely applied to the fields of electronic components, microcomputer control boards and the like as a potting material, and plays roles of overload resistance and electronic component protection.
The polyurea is composed of isocyanate component (R-N ═ C ═ O) and amino compound (R-NH)2) The reaction principle and the molecular structure are shown in figure 1. As can be seen from the molecular structure, polyurea is a microphase-separated block polymer material and is composed of a hard segment and a soft segment, wherein the hard segment is generally connected with a strongly polar urea bond containing (-NH-CO-NH-) segment connected by a hydrogen bond, and the glass transition temperature (Tg) of the polyurea is higher than the ambient temperature; the soft segments consist of aliphatic segments of relatively good flexibility and have a Tg below ambient temperature, usually below-30 ℃. Thus, polyurea is a typical microphase-dispersed thermoplastic cross-linked polymer at ambient temperatures. The highly complex internal microstructure of polyurea allows polyurea to exhibit stable chemical properties and excellent overall mechanical properties on a macroscopic scale.
The mechanical property of polyurea is influenced by various factors, such as the content ratio of soft and hard segments. With the increase of hard sections in the polyurea, the polyurea is changed from a soft rubber state to a hard plastic state, so that the comprehensive mechanical property of the polyurea is increased, but the density is increased, so that the using effect and the application range of the polyurea are limited, and the polyurea is particularly not favorable for encapsulating and protecting electronic components in the fields of aviation, aerospace, missile loading and the like. As the soft segment in the polyurea is increased, the density of the polyurea is reduced, so that the mechanical property is reduced, and the application range are limited.
Disclosure of Invention
The invention aims to provide high-overload-resistant light polyurea and a preparation method thereof, and aims to solve the problem that the use effect and range of the low-density polyurea are limited due to the fact that the mechanical property of the low-density polyurea is weak due to the limitation of the internal structure of the existing polyurea.
In order to achieve the above object, the present invention provides a technical solution, which comprises an amino compound, a light filler and isocyanate, wherein the amino compound comprises a curing agent, a chain extender and an organic solvent.
The beneficial effects of the technical scheme are as follows:
according to the technical scheme, the polyurea with better mechanical property is obtained by adjusting different raw materials. The added light filler limits the motion of a high molecular chain segment, so that the polyurea material with more excellent mechanical property is obtained, and the polyurea material is more widely applied to the field of electronic component protection.
Further, the curing agent is polyether amine; the chain extender is phenylenediamine, m-phenylenediamine or diamine; the organic solvent is formamide, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc).
Has the advantages that: by setting the curing agent, the chain extender and the organic solvent, the mechanical property of the prepared polyurea can be effectively improved.
Further, the mass of the organic solvent in the amino compound is 0.1-0.5% of the total mass of the curing agent and the chain extender, and the mass ratio of the curing agent to the chain extender is 1:2-8: 1.
Has the advantages that: the mechanical property of the prepared polyurea is good by matching the amount of each raw material for preparing the amino compound.
Further, the mass of the light filler is 0-100% of the total mass of the curing agent and the chain extender.
Has the advantages that: the amount of the light filler is configured, so that the light filler can be used for limiting the movement of a high molecular chain segment, and the prepared polyurea has excellent mechanical property; meanwhile, through the limitation on the proportion, the uniform mixing of the light filler can be realized, the uniform density of each part is realized, and the good mechanical property of the polyurea is further ensured.
Further, the light filler is one or a mixture of more of graphene, carbon nanotubes, hollow glass particles and hollow ceramic particles, and the particle size of the light filler is below micron level.
Has the advantages that: the polyurea prepared by configuring the type and the particle size of the light filler has better mechanical property.
Further, the ratio of the amount of the isocyanate group-containing substance to the amount of the amino group-containing substance is 1:2 to 2: 1.
Has the advantages that: by proportioning the amounts of the isocyanate and the amino compound, the polyurea with better mechanical property can be fully fused.
Further, isocyanate refers to a substance containing a functional group of — N ═ C ═ O, including monoisocyanates R — N ═ C ═ O and diisocyanates O ═ C ═ N-R-N ═ C ═ O and polyisocyanates; the isocyanate is Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl isocyanate (PAPI).
Has the advantages that: the mechanical property of the prepared polyurea is good by setting the type of the isocyanate.
The invention also provides another technical scheme, and the preparation method of the high-overload-resistant light polyurea is characterized by comprising the following steps of:
s1, adding the chain extender into the curing agent, and fully mixing with an organic solvent to obtain amino compound components with different molecular weights;
s2, adding a light filler into the amino compound component prepared in the step S1, and stirring at the rotating speed of 60-120rpm for 12-24h to form a blend;
s3, adding isocyanate into the blend, and synchronously and rapidly stirring for 20-30S to obtain high-viscosity fluid;
s4, pouring the high-viscosity fluid prepared in the step S3 into a mold, and standing for 12-24 hours at room temperature to completely cure the high-overload resistant light polyurea.
The beneficial effects of the technical scheme are as follows:
the viscosity is increased sharply after the polyurea double-component is mixed, the fluidity of the low-density filler in the curing reaction process is reduced, and the phenomenon of uneven density distribution of the filler due to gravity floating is avoided. The encapsulating material with low density, high strength and high solid content is prepared by filling light-weight filler into bi-component raw materials (polyether amine and isocyanate component materials) for synthesizing polyurea for the first time by adopting formula design and process optimization. In addition, in the aspect of a forming process, the requirements of different encapsulated parts can be met through diversified forming modes.
Further, in step S2, the light filler is modified by using 0.5-2 wt% silane coupling agent solution, and then added into the amino compound.
Has the advantages that: before the preparation, the light filler is modified, so that the mechanical property of the prepared polyurea is better.
Further, the stirring manner in step S3 is to rotate and stir for 20-30S in one direction at a rotation speed of 120-200 rpm.
Has the advantages that: through setting up the stirring mode, can realize the homogeneous mixing between each material.
The mechanical properties of polyurea are influenced by multiple factors, such as the content ratio of soft and hard segments, the loading rate, the temperature, etc., and in order to change the mechanical properties of polyurea, the most common way is to change the content ratio of soft and hard segments. By adding the hard section, the polyurea can be converted from a soft rubber state to a hard plastic state, so that the comprehensive mechanical property of the polyurea is improved; however, excessive hard segment content will reduce the comprehensive mechanical properties of polyurea and is not favorable for the use of polyurea. Meanwhile, the increase of the hard section can increase the density of the polyurea, and the high-density polyurea can limit the use effect and the use range, especially in the fields of aviation, aerospace, missile-borne and the like which need light materials.
Therefore, the inventor abandons the traditional way of increasing the hard segment and develops the soft polyurea, and as the soft segment in the polyurea is increased, the density of the polyurea is reduced, so the mechanical property is reduced, and the application range are limited. In the process of research and development, the inventor overcomes the technical problem, and prepares the light polyurea through the coincidence of isocyanate, amino compound and light filler, the comprehensive mechanical property of the light polyurea can meet the use requirement, and the light polyurea has low density and can be widely applied.
In conclusion, the isocyanate component and the amino compound component are rapidly mixed and reacted, and are filled with light-weight high-strength filler, so that the obtained double-component high-solid-content one-step forming material with the density lower than 1g/cm is obtained at room temperature3The polyurea filling and sealing material can effectively buffer overload of over 20000g and has excellent comprehensive mechanical properties. The method has the advantages of simple curing process, strong bonding force, good static/dynamic mechanical properties and the like. No by-product is produced in the whole process, and a process flow with high efficiency, no pollution and low cost can be brought. The technical scheme proves the operability of manufacturing the light polyurea and the feasibility of using the light polyurea as the encapsulating material, and widens the material variety and the application field of the polyurea.
Drawings
FIG. 1 is a diagram illustrating the reaction principle and molecular structure of polyurea in the prior art;
FIG. 2 is a graph showing the infrared contrast of the overload resistant light polyurea and epoxy resin prepared according to the present invention;
FIG. 3 is a scanning electron microscope cross-sectional view of the overload-resistant light polyurea (soft hard polyurea) provided by the present invention;
FIG. 4 is a scanning electron micrograph of a cross section of a soft polyurea for comparison;
FIG. 5 is a graph of tensile strength and elongation at break for 3 experimental samples;
fig. 6 is a compressive stress-strain curve for 3 sets of samples.
Detailed Description
The following is further detailed by way of specific embodiments:
a high-overload-resistant light polyurea comprises an amino compound, a light filler and isocyanate, wherein the amino compound comprises a curing agent, a chain extender and an organic solvent. Wherein the mass of the organic solvent in the amino compound is 0.1-0.5% of the total mass of the curing agent and the chain extender, and the mass ratio of the curing agent to the chain extender is 1:2-8: 1; the mass of the light filler is 0-100% of the total mass of the curing agent and the chain extender; the ratio of the amount of the substance containing isocyanate groups to the amount of the substance containing amino groups is 1:2 to 2: 1.
The curing agent is polyether amine; the chain extender is phenylenediamine, m-phenylenediamine or diamine; the organic solvent is formamide, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc).
Isocyanates are those containing functional groups — N ═ C ═ O, including monoisocyanates R — N ═ C ═ O and diisocyanates O ═ C ═ N-R-N ═ C ═ O and polyisocyanates; the isocyanate is Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl isocyanate (PAPI).
The light filler is one or a mixture of more of graphene, carbon nano tubes, hollow glass particles and hollow ceramic particles, and the light filler is particles with the particle size below micron level.
A preparation method of high-overload-resistant light polyurea comprises the following steps:
s1, adding the chain extender into the curing agent according to the proportion, adding the organic solvent, and fully stirring to obtain amino compound components with different molecular weights for later use.
S2, weighing the light filler according to the proportion, modifying the light filler by using 0.5-2 wt% of silane coupling agent solution, and drying for later use.
Adding the modified light filler into the amino compound component, and stirring for 12-24h at the rotating speed of 60-12rpm to uniformly disperse the light filler in the amino compound component to form a blend for later use.
S3, weighing the isocyanate according to the proportion, putting the weighed isocyanate into the blend, and synchronously and rapidly stirring for 20-30S to enable the viscosity of the fluid to be increased rapidly to obtain the high-viscosity fluid.
And S4, pouring the high-viscosity fluid prepared in the S3 into a mold, and standing for 12-24 hours at room temperature to completely cure the high-overload resistant light polyurea to obtain the high-overload resistant light polyurea.
The following experiments were carried out according to the parameters described below, and the results of the experiments were recorded.
The curing agent and the chain extender in the amino compound are polyether amine D2000 and m-phenylenediamine, and the ratio of the prepared substances is 8: two samples of 1 and 8: 9. The mass of the organic solvent in the two samples is 0.2 percent of the total mass of the curing agent and the chain extender, and the light filler is hollow glass beads with the particle size of 85 mu m. Before polyurea is mixed as a filler, a surface modification treatment with a silane coupling agent is required. The isocyanate is isophorone diisocyanate (IPDI), and the quantity ratio of the isocyanate to the amino compound is 1: 1. The 1#, 9# samples in the following experiments represent polyureas with curing agent and chain extender material in the 8:1 and 8:9 ratio, respectively. Light-9 # represents the addition of hollow glass beads having a particle size of 85 μm and a mass percentage of 15% to polyurea having an amount ratio of curing agent to chain extender material of 8: 1.
1. Structural unit analysis
The Polyurea (PU) provided by the present invention was infrared-compared with the epoxy resin (EP), and the results are shown in FIG. 2. As can be seen from FIG. 2, the characteristic peak position of the epoxy resin is typically 1602cm-1And 1502cm-1The skeletons ascribed to C ═ C and C — C on the benzene ring vibrate. At 1012cm-1The corresponding characteristic peak is the stretching vibration of the ether C-O-C in the structural unit; at 924cm-1And 831cm-1The positions correspond to the stretching vibration of C-O and C-O-C in the terminal epoxy group respectively.
While polyurea, the typical characteristic peak position is 1638cm-1The stretching vibration at C ═ O is attributed to the hydrogen-bonded urea carbonyl group. Secondly, 1545cm-1The stretching vibration corresponding to C-N and the bending vibration corresponding to N-H are superposed at 3348cm-1And has N-H stretching vibration peak to form hydrogen bond. In comprehensive comparison, the structural unit of the polyurea is obviously different from the structural unit of the epoxy resin, and the polyurea structural unit has obvious hydrogen bond effect, so that the polyurea has positive effect on improving the mechanical property of the material, and therefore, the polyurea provided by the invention has better mechanical property than the epoxy resin.
2. Topography analysis
The light polyurea soft is obtained by compounding the isocyanate group and the amino group, and the light polyurea (namely the high-overload-resistant light polyurea provided by the invention) is obtained by compounding the isocyanate group, the amino group and the light filler.
Scanning electron micrographs of the sections of the 1# Hard Polyurea (HPU) and the 9# Soft Polyurea (SPU) at 70 times and 15000 times are shown in FIG. 3 and FIG. 4, respectively. Under the condition that the ratio of isocyanate groups to amino groups is 1.05:1, the relative content of hard segments and soft segments in a molecular chain is adjusted by changing the relative content of a curing agent and a chain extender. Wherein, the more the hard segment content is, the more the comprehensive performance of the material tends to be hard and tough, the higher the density of the material is, the 1# polyurea leads the density of the material to be 0.9728-1.0383g/cm3And increases as the content of the chain extender increases. While the density of the light-9 # polyurea material can be reduced to 0.75g/cm by compounding the hollow glass beads with low density3Thereby obtaining light and hard polyurea. As can be seen from the comparison between FIG. 3 and FIG. 4, the 1# hard polyurea has more compact particle packing, relatively regular cross-sectional stripes and better mechanical properties than the 9# soft polyurea, although the density of the soft polyurea is lower than that of the hard polyurea. Therefore, there is a need to adjust the mechanical properties of the soft polyurea by adding fillers.
3. Analysis of tensile Properties
The tensile strength test was performed on 3 test groups, and the tensile strength and elongation at break of the 3 test groups are shown in fig. 5. According to the formula shown in fig. 5, in the formula design, the relative content of the soft segment and the hard segment in the molecular chain is changed through the relative content of the chain extender, so that the strength of the hydrogen bond effect of the material is controlled, the hardness and softness of the overall performance of the material can be regulated, and the application range of the polyurea material in different environments is widened. The 1# hard polyurea had higher tensile strength (8.2MPa), excellent elongation (218.8%), while the 9# soft polyurea had higher elongation (308.7%), but low ultimate tensile strength (1.96 MPa). The ultimate tensile strength of the soft polyurea (increased from 1.96MPa to 4.69MPa) can be enhanced by adding the glass bead filler to the No. 9 soft polyurea, but the toughness is not affected, and the elongation is still maintained at 298.5%.
4. Compression performance analysis
Young modulus of 9#, 1#, light-9 # polyurea and epoxy resin in an elastic deformation area are 3.272MPa, 8.963MPa, 18.259MPa and 137.770MPa respectively; as can be seen from fig. 6, the strain of the epoxy resin is smaller than that of the hard polyurea in the same environment under the same stress. Polyurea materials generally have a lower modulus than epoxy resins due to differences in the inherent properties of the structural units and the material. This deficiency can be compensated by adding inorganic fillers (e.g., lightweight hollow glass beads) to restrict the movement of the polymer segments. As shown, the addition of hollow glass bead filler to # 9 soft polyurea was effective in increasing the Young's modulus of the polyurea (from 3.272MPa to 8.963 MPa).
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and these changes and modifications should not be construed as affecting the performance of the invention and its practical application.
Claims (10)
1. A high-overload-resistant light polyurea is characterized in that: comprises an amino compound, a light filler and isocyanate, wherein the amino compound comprises a curing agent, a chain extender and an organic solvent.
2. The high overload resistant light polyurea of claim 1 wherein: the curing agent is polyether amine; the chain extender is phenylenediamine, m-phenylenediamine or diamine; the organic solvent is formamide, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc).
3. The high overload resistant light polyurea of claim 2 wherein: the mass of the organic solvent in the amino compound is 0.1-0.5% of the total mass of the curing agent and the chain extender, and the mass ratio of the curing agent to the chain extender is 1:2-8: 1.
4. The high overload resistant light polyurea of claim 3 wherein: the mass of the light filler is 0-100% of the total mass of the curing agent and the chain extender.
5. The high overload resistant light polyurea of claim 4 wherein: the light filler is one or a mixture of more of graphene, carbon nanotubes, hollow glass particles and hollow ceramic particles, and the particle size of the light filler is below micron level.
6. The high overload resistant light polyurea of claim 5 wherein: isocyanic acid substance (-NCO) and amino compound substance (-NH)2) The mass ratio of (A) to (B) is 1:2 to 2: 1.
7. The high overload resistant light polyurea of claim 6 wherein: isocyanates are those containing functional groups — N ═ C ═ O, including monoisocyanates R — N ═ C ═ O and diisocyanates O ═ C ═ N-R-N ═ C ═ O and polyisocyanates; the isocyanate is Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl isocyanate (PAPI).
8. The method for preparing the high overload resistant light polyurea according to any one of claims 1 to 7, characterized by comprising the following steps:
s1, adding the chain extender into the curing agent, and fully mixing with an organic solvent to obtain amino compound components with different molecular weights;
s2, adding a light filler into the amino compound component prepared in the step S1, and stirring at the rotating speed of 60-120rpm for 12-24h to form a blend;
s3, adding isocyanate into the blend, and synchronously and rapidly stirring for 20-30S to obtain high-viscosity fluid;
s4, pouring the high-viscosity fluid prepared in the step S3 into a mold, and standing for 12-24 hours at room temperature to completely cure the high-overload resistant light polyurea.
9. The preparation method of the high overload resistant light polyurea according to claim 8, wherein the method comprises the following steps: in step S2, the light filler is modified by 0.5-2 wt% silane coupling agent solution and then added into the amino compound.
10. The preparation method of the high overload resistant light polyurea according to claim 9, characterized in that: the stirring manner in step S3 is to stir by rotating in one direction for 20 to 30 seconds.
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| CN115873291A (en) * | 2022-12-23 | 2023-03-31 | 郑州圣莱特空心微珠新材料有限公司 | Substitute wood and preparation method thereof |
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