CN110818877A - PEEK-nanometer SiO2Composite doped polyurethane foam buoyancy material - Google Patents
PEEK-nanometer SiO2Composite doped polyurethane foam buoyancy material Download PDFInfo
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- 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
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- 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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
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- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
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- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to the technical field of foam composite materials, and discloses PEEK-nanometer SiO2Composite doping typeThe polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 15-25 parts of Toluene Diisocyanate (TDI) and 3-8 parts of surface modified nano SiO2The paint comprises particles, 3-5 parts of polyether ether ketone (PEEK), 0.96-1.5 parts of triethanolamine, 0.6-0.9 part of organic silicon oil foam stabilizer, 2-3 parts of ultrapure water, 0.32-0.5 part of triethylene diamine and 0.096-0.15 part of stannous octoate; the preparation of the polyurethane foam buoyancy material comprises the following steps: to nano SiO2And carrying out surface modification on the particles, and carrying out foaming reaction on the particles, polyether ether ketone powder, Toluene Diisocyanate (TDI) and triethanolamine under the action of a foaming agent to prepare the polyurethane foam buoyancy material. The invention solves the technical problems that the wall of the bubble hole can be broken and seeped and lose buoyancy under shallow water due to lower compression strength of the existing foam composite buoyancy material.
Description
Technical Field
The invention relates to the technical field of foam composite materials, in particular to PEEK-nanometer SiO2Composite doped polyurethane foam buoyancy material。
Background
The chemical foaming buoyancy material is a foam composite material prepared by a chemical foaming method, namely, a chemical foaming agent is decomposed by resin curing heat to generate gas, the gas is dispersed in resin to be foamed, and then the foam composite material is cast and molded. Although the chemical foaming buoyancy material can obtain ideal density (the lowest density can reach 0.008 g/cm)3) However, the material has low compressive strength, and the cell wall of the material can be broken and seeped under shallow water, so that the buoyancy is lost, and the use reliability is poor.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides PEEK-nanometer SiO2The composite doped polyurethane foam buoyancy material aims at solving the technical problems that the wall of a foam hole can be broken and seeped under shallow water and lose buoyancy due to low compression strength of the existing foam composite buoyancy material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
PEEK-nanometer SiO2The composite doped polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 15-25 parts of Toluene Diisocyanate (TDI) and 3-8 parts of surface modified nano SiO2The paint comprises particles, 3-5 parts of polyether ether ketone (PEEK), 0.96-1.5 parts of triethanolamine, 0.6-0.9 part of organic silicon oil foam stabilizer, 2-3 parts of ultrapure water, 0.32-0.5 part of triethylene diamine and 0.096-0.15 part of stannous octoate;
the preparation of the polyurethane foam buoyancy material comprises the following steps: to nano SiO2And carrying out surface modification on the particles, and carrying out foaming reaction on the particles, polyether ether ketone powder, Toluene Diisocyanate (TDI) and triethanolamine under the action of a foaming agent to prepare the polyurethane foam buoyancy material.
Further, the average particle size of the polyether ether ketone Powder (PEEK) is less than or equal to 10 um; the nano SiO2The particles comprise: 100 parts of SiO with the average grain diameter less than or equal to 100nm270 parts of a mixture having an average particle diameter of not more than 50nmSiO2。
Preferably, the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 25g of Toluene Diisocyanate (TDI), 8g of surface-modified nano SiO2The paint comprises particles, 5g of polyether ether ketone (PEEK) with the average particle size of less than or equal to 10um, 1.5g of triethanolamine, 0.6g of silicone oil foam stabilizer, 3g of ultrapure water, 0.32g of triethylene diamine and 0.15g of stannous octoate.
Preferably, the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 18g of Toluene Diisocyanate (TDI), 5g of surface-modified nano SiO2The paint comprises particles, 5g of polyether ether ketone (PEEK) with the average particle size of less than or equal to 10um, 1g of triethanolamine, 0.9g of silicone oil foam stabilizer, 2g of ultrapure water, 0.5g of triethylene diamine and 0.12g of stannous octoate.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the invention is prepared by the reaction of nano SiO2Carrying out surface modification on the particles, and carrying out foaming reaction on the particles, polyether ether ketone powder, Toluene Diisocyanate (TDI) and triethanolamine under the action of a foaming agent to prepare the polyurethane foam buoyancy material, wherein the density of the polyurethane foam buoyancy material is 0.20-0.24 g/cm3The compressive strength is 86-90 MPa;
and the density of the polyurethane foam buoyancy material prepared in the comparative example is 0.18g/cm3Compared with the polyurethane foam buoyancy material with the compression strength of 72MPa, the polyurethane foam buoyancy material has the advantages that the density of the polyurethane foam buoyancy material is basically consistent, and meanwhile, the technical effect of remarkably improving the compression strength of the polyurethane foam buoyancy material is achieved;
therefore, the technical problems that the wall of the bubble hole can be broken and seeped and lose buoyancy under shallow water due to lower compression strength of the existing foam composite buoyancy material are solved.
Detailed Description
Surface modified nano SiO2The particles were prepared as follows:
100g of SiO with the average grain diameter less than or equal to 100nm270g of average particle diameterSiO of less than or equal to 50nm2Drying in a 120 ℃ oven for 2 h;
drying the two types of nano SiO with different particle diameters2Dispersing in 500mL xylene solution, ultrasonic dispersing for 30min, magnetically stirring for 30min, and adding N2Dropping 100g of r-aminopropyl triethoxysilane coupling agent and 2g of triethylamine under protection, heating to 130 ℃ for reaction for 12h, then extracting with 500mL of absolute ethanol at 100 ℃ for 48h, and drying for later use to obtain surface-modified nano SiO2Particles;
the first embodiment is as follows:
the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 20g of Toluene Diisocyanate (TDI), 5g of surface-modified nano SiO2Particles, 3g of polyether ether ketone (PEEK) powder with the average particle size of less than or equal to 10um, 0.96g of triethanolamine, 0.6g of silicone oil foam stabilizer, 2g of ultrapure water, 0.32g of triethylene diamine and 0.096g of stannous octoate;
the preparation method of the polyurethane foam buoyancy material comprises the following steps:
the method comprises the following steps: taking 20g of Toluene Diisocyanate (TDI) as a component I;
step two: taking 5g of surface modified nano SiO2The components are uniformly stirred and mixed to form a component II, wherein the component II comprises 3g of polyether ether ketone (PEEK) with the average particle size of less than or equal to 10um, 0.96g of triethanolamine, 0.6g of silicone oil foam stabilizer, 2g of ultrapure water, 0.32g of triethylene diamine and 0.096g of stannous octoate;
step three: and adding the component I into the component II, mechanically stirring at a high speed of 1500rpm for 10s, pouring into a mold, freely foaming at a temperature of 25 ℃, and curing for 1h to prepare the polyurethane foam buoyancy material.
Example two:
the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 15g of Toluene Diisocyanate (TDI), 3g of surface-modified nano SiO24g of polyether ether ketone (PEEK) powder with the average particle diameter less than or equal to 10um, 0.96g of triethanolamine, 0.8g of silicone oil foam stabilizer and 3g of silicone oil foam stabilizerUltrapure water, 0.4g of triethylene diamine and 0.1g of stannous octoate;
the preparation method of the polyurethane foam buoyancy material comprises the following steps:
the method comprises the following steps: taking 15g of Toluene Diisocyanate (TDI) as a component I;
step two: taking 3g of surface modified nano SiO2Particles, 4g of polyether ether ketone (PEEK) powder with the average particle size of less than or equal to 10um, 0.96g of triethanolamine, 0.8g of silicone oil foam stabilizer, 3g of ultrapure water, 0.4g of triethylene diamine and 0.1g of stannous octoate are stirred and mixed uniformly to form a component II;
step three: and adding the component I into the component II, mechanically stirring at a high speed of 1500rpm for 8s, pouring into a mold, freely foaming at a temperature of 25 ℃, and curing for 1h to prepare the polyurethane foam buoyancy material.
Example three:
the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 25g of Toluene Diisocyanate (TDI), 8g of surface-modified nano SiO2Particles, 5g of polyether ether ketone (PEEK) powder with the average particle size of less than or equal to 10um, 1.5g of triethanolamine, 0.6g of silicone oil foam stabilizer, 3g of ultrapure water, 0.32g of triethylene diamine and 0.15g of stannous octoate;
the preparation method of the polyurethane foam buoyancy material comprises the following steps:
the method comprises the following steps: taking 25g of Toluene Diisocyanate (TDI) as a component I;
step two: taking 8g of surface modified nano SiO2The components are uniformly stirred and mixed to form a component II, wherein the component II comprises 5g of polyether ether ketone (PEEK) powder with the average particle size of less than or equal to 10um, 1.5g of triethanolamine, 0.6g of silicone oil foam stabilizer, 3g of ultrapure water, 0.32g of triethylene diamine and 0.15g of stannous octoate;
step three: and adding the component I into the component II, mechanically stirring at a high speed of 1500rpm for 15s, pouring into a mold, freely foaming at the temperature of 25 ℃, and curing for 1h to prepare the polyurethane foam buoyancy material.
Example four:
the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 18g of Toluene Diisocyanate (TDI), 5g of surface-modified nano SiO2Particles, 5g of polyether ether ketone (PEEK) powder with the average particle size of less than or equal to 10um, 1g of triethanolamine, 0.9g of silicone oil foam stabilizer, 2g of ultrapure water, 0.5g of triethylene diamine and 0.12g of stannous octoate;
the preparation method of the polyurethane foam buoyancy material comprises the following steps:
the method comprises the following steps: taking 18g of Toluene Diisocyanate (TDI) as a component one;
step two: taking 5g of surface modified nano SiO2Particles, 5g of polyether ether ketone (PEEK) powder with the average particle size of less than or equal to 10um, 1g of triethanolamine, 0.9g of silicone oil foam stabilizer, 2g of ultrapure water, 0.5g of triethylene diamine and 0.12g of stannous octoate are uniformly stirred and mixed to form a component II;
step three: and adding the component I into the component II, mechanically stirring at a high speed of 1500rpm for 15s, pouring into a mold, freely foaming at the temperature of 25 ℃, and curing for 1h to prepare the polyurethane foam buoyancy material.
Comparative example:
the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 20g of Toluene Diisocyanate (TDI), 0.96g of triethanolamine, 0.6g of silicone oil foam stabilizer, 2g of ultrapure water, 0.32g of triethylene diamine, and 0.096g of stannous octoate;
the preparation method of the polyurethane foam buoyancy material comprises the following steps:
the method comprises the following steps: taking 20g of Toluene Diisocyanate (TDI) as a component I;
step two: taking 0.96g of triethanolamine, 0.6g of silicone oil foam stabilizer, 2g of ultrapure water, 0.32g of triethylene diamine and 0.096g of stannous octoate, and uniformly stirring and mixing to obtain a component II;
step four: and adding the component I into the component II, mechanically stirring at a high speed of 1500rpm for 10s, pouring into a mold, freely foaming at a temperature of 25 ℃, and curing for 1h to prepare the polyurethane foam buoyancy material.
And (3) performance testing:
the polyurethane foam buoyancy materials prepared in the above examples and comparative examples were subjected to performance tests, and the test results are shown in table 1 below.
TABLE 1
| Examples | Density (g/cm)3) | Compressive Strength (MPa) |
| Example one | 0.24 | 86 |
| Example two | 0.24 | 88 |
| EXAMPLE III | 0.22 | 90 |
| Example four | 0.20 | 89 |
| Comparative example | 0.18 | 72 |
Claims (4)
1. PEEK-nanometer SiO2The composite doped polyurethane foam buoyancy material is characterized by comprising the following raw materials in parts by weight: 15-25 parts of Toluene Diisocyanate (TDI) and 3-8 parts of surface modified nano SiO2The paint comprises particles, 3-5 parts of polyether ether ketone (PEEK), 0.96-1.5 parts of triethanolamine, 0.6-0.9 part of organic silicon oil foam stabilizer, 2-3 parts of ultrapure water, 0.32-0.5 part of triethylene diamine and 0.096-0.15 part of stannous octoate;
the preparation of the polyurethane foam buoyancy material comprises the following steps: to nano SiO2And carrying out surface modification on the particles, and carrying out foaming reaction on the particles, polyether ether ketone powder, Toluene Diisocyanate (TDI) and triethanolamine under the action of a foaming agent to prepare the polyurethane foam buoyancy material.
2. The polyurethane foam buoyancy material of claim 1, wherein the polyether ether ketone Powder (PEEK) has an average particle size of 10um or less; the nano SiO2The particles comprise: 100 parts of SiO with the average grain diameter less than or equal to 100nm270 parts of SiO with the average particle size of less than or equal to 50nm2。
3. The polyurethane foam buoyancy material according to claim 2, wherein the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 25g of Toluene Diisocyanate (TDI), 8g of surface-modified nano SiO2The paint comprises particles, 5g of polyether ether ketone (PEEK) with the average particle size of less than or equal to 10um, 1.5g of triethanolamine, 0.6g of silicone oil foam stabilizer, 3g of ultrapure water, 0.32g of triethylene diamine and 0.15g of stannous octoate.
4. The polyurethane foam buoyancy material according to claim 2, wherein the polyurethane foam buoyancy material comprises the following raw materials in parts by weight: 18g of Toluene Diisocyanate (TDI), 5g of surface-modified nano SiO2Granules, 5g of polyether ether ketone (PEEK) powder with the average particle diameter less than or equal to 10um, 1g of triethanolamine, 0.9g of silicone oil foam stabilizer, 2g of ultrapure water, 0.5g of triethylene diamine and 0.12g of stannous octoate.
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