CN113583429B - Preparation method of polyurethane composite material for building - Google Patents
Preparation method of polyurethane composite material for building Download PDFInfo
- Publication number
- CN113583429B CN113583429B CN202111058444.7A CN202111058444A CN113583429B CN 113583429 B CN113583429 B CN 113583429B CN 202111058444 A CN202111058444 A CN 202111058444A CN 113583429 B CN113583429 B CN 113583429B
- Authority
- CN
- China
- Prior art keywords
- parts
- stirring
- nano
- water
- montmorillonite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 35
- 239000004814 polyurethane Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 59
- 238000001723 curing Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920002678 cellulose Polymers 0.000 claims abstract description 32
- 239000001913 cellulose Substances 0.000 claims abstract description 32
- 239000004964 aerogel Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 26
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 21
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 21
- 235000005822 corn Nutrition 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000010902 straw Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 14
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 14
- 239000005011 phenolic resin Substances 0.000 claims abstract description 14
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 14
- 229940018333 calcium pyruvate Drugs 0.000 claims abstract description 13
- UZWMCCLZMHPPKW-UHFFFAOYSA-L calcium;2-oxopropanoate Chemical compound [Ca+2].CC(=O)C([O-])=O.CC(=O)C([O-])=O UZWMCCLZMHPPKW-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 30
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 240000008042 Zea mays Species 0.000 claims description 19
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 15
- 239000000347 magnesium hydroxide Substances 0.000 claims description 15
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004566 building material Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 12
- 230000008014 freezing Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims 1
- 241000209149 Zea Species 0.000 abstract 2
- 239000000463 material Substances 0.000 description 12
- 239000000779 smoke Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 automobile factory Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a polyurethane composite material for buildings, which comprises the following components in parts by weight: 20-30 parts of polyurethane resin, 12-18 parts of cellulose aerogel, 6-12 parts of modified montmorillonite, 1-2 parts of dibutyltin dilaurate, 8-10 parts of corn straw, 6-10 parts of phenolic resin and 3-5 parts of ethylenediamine. The preparation method comprises the steps of crushing the corn straws into aggregates with different thicknesses of 15-30 mm, adding the aggregates into a sulfuric acid solution, soaking for 2-3 h, filtering, washing with water, drying, adding the aggregates into a mixed solution of water, a nano-silica solution, calcium pyruvate and dimethylformamide, stirring for 3-5 h, fishing out, drying at 75-80 ℃, mixing and stirring with polyurethane resin, cellulose aerogel, modified montmorillonite, dibutyltin dilaurate, phenolic resin and ethylenediamine according to the proportion, wherein the stirring temperature is 80-90 ℃, the rotation speed is 450-600 rpm/min, and the stirring reaction time is 20-40 min; and pouring the mixture after the stirring reaction into a mold, curing and molding, and cooling and demolding to obtain the polyurethane composite material.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a preparation method of a polyurethane composite material for buildings.
Background
The polyurethane material is prepared by the polymerization reaction of polyol and polyisocyanate, different structures and properties can be obtained by utilizing different raw materials, and finally products such as coatings, adhesives, plastics, fibers, rubber and the like from liquid to solid and from soft to hard can be prepared, so that the application is very wide and the application range is rapidly increased. The polyurethane rigid foam plastic material is an important component of a polyurethane product, and has the advantages of rich raw materials, simple and convenient preparation process, excellent comprehensive performance, wide application range and the like compared with other foam plastics. In addition, the extremely low thermal conductivity coefficient is a great advantage of the material, and can reach about 0.025W/K.m, so that the material becomes the heat-insulating material with the best use effect at present.
At present, polyurethane materials are used in building materials, the production capacity of the polyurethane materials is increasing, the polyurethane materials have the advantages of large hardness, high compression strength, good dimensional stability, light weight, low thermal conductivity, high closed porosity (above 95%), good corrosion resistance, good wear resistance and the like, the polyurethane materials also have wide application, can replace materials such as rubber, plastic, nylon and the like, and are used for airport, hotel, building materials, automobile factory, coal mine factory, cement factory, high-level apartment, villa, garden beautification and the like. However, the polyurethane composite material belongs to a flammable material, and toxic gases such as HCN, CO and the like are released in the combustion process, which brings great difficulty to fire extinguishment and escape from fire scenes.
Disclosure of Invention
Aiming at the problems that the polyurethane composite material in the prior art is inflammable, has large smoke quantity after combustion, and generates gases such as HCN, CO and the like. The invention aims to provide a preparation method of a polyurethane composite material for buildings, wherein the building material comprises the following components in parts by weight: 20-30 parts of polyurethane resin, 12-18 parts of cellulose aerogel, 6-12 parts of modified montmorillonite, 1-2 parts of dibutyltin dilaurate, 8-10 parts of corn straw, 6-10 parts of phenolic resin and 3-5 parts of ethylenediamine.
The preparation method comprises the following steps:
s1: crushing corn stalks into aggregates with different thicknesses of 15-30 mm, adding the aggregates into a sulfuric acid solution, soaking for 2-3 h, filtering, washing with water, drying, adding the aggregates into a mixed solution of water, a nano-silica solution, calcium pyruvate and dimethylformamide, stirring for 3-5 h, fishing out, and drying at 75-80 ℃ for later use.
S2: mixing and stirring the corn straws, the polyurethane resin, the cellulose aerogel, the modified montmorillonite, the dibutyltin dilaurate, the phenolic resin and the ethylenediamine in the step S1 according to the proportion, wherein the stirring temperature is 80-90 ℃, the rotating speed is 450-600 rpm/min, and the stirring reaction time is 20-40 min.
S3: and (3) pouring the mixture stirred and reacted in the step (S2) into a mold, curing and molding, cooling and demolding to obtain the polyurethane composite material.
Preferably, the mass-to-volume ratio of the water, the nano-silica solution, the calcium pyruvate and the dimethylformamide is (100-150) mL, (4.2-6.8) mL, (1.3-1.9) g, (10-16) mL.
Preferably, the curing and forming in the step S3 is divided into three stages, the curing temperature of the first stage is 140 to 150 ℃, and the curing time is 2 to 3 hours; the curing temperature of the second stage is 220-230 ℃, and the curing time is 2.5-4 h; the curing temperature of the third stage is 255-270 ℃, and the curing time is 1-1.5 h.
Preferably, the cellulose aerogel is prepared by the following method:
1) Adding cellulose nano-fiber into water, stirring at high speed for 5-8 h to obtain suspension I, adding nano-montmorillonite into water, stirring at high speed to disperse the nano-montmorillonite to obtain suspension II, mixing the suspension I and the suspension II, and stirring for 6-9 h for later use.
2) Freezing the suspension mixed liquor obtained in the step 1) for 25-40 min at the temperature of-50 to-65 ℃, and then freezing and drying for 45-60 h in a liquid nitrogen environment to obtain the cellulose aerogel.
Preferably, the modified montmorillonite is prepared by the following method:
the method comprises the following steps: mixing nano montmorillonite, expanded graphite, aluminum hydroxide and magnesium hydroxide uniformly, adding the mixture into distilled water, ultrasonically stirring the mixture for 10 to 15min, then adding an ammonia water solution to adjust the pH value to 10.5 to 11.5, and stirring the mixture for later use.
Step two: and (3) moving the mixed solution in the step one to a high-pressure reaction kettle, then placing the mixed solution in an oven, reacting for 5-8 h at 210-230 ℃, cooling, washing with distilled water for three times, and drying at 80-90 ℃ to obtain the modified montmorillonite.
More preferably, the mass ratio of the nano montmorillonite, the expanded graphite, the aluminum hydroxide and the magnesium hydroxide is (1-2): (0.4-0.75): (0.42-0.78): (0.36-0.69).
The invention has the following beneficial effects:
1. according to the invention, the prepared polyurethane composite material has excellent mechanical properties, excellent heat insulation performance and flame retardant performance, and has the maximum smoke density of below 38, excellent smoke generation amount and less toxic gas generation.
2. In the invention, the montmorillonite is modified by adopting expanded graphite, aluminum hydroxide and magnesium hydroxide to obtain the modified montmorillonite, wherein the aluminum hydroxide and the magnesium hydroxide are attached to the surface of the expanded graphite after the montmorillonite is modified, and the aluminum hydroxide and the magnesium hydroxide are compounded with the montmorillonite to play a role in flame retardance and influence the structure of a high molecular material, reduce the combustion smoke generation amount of the high molecular material and improve the mechanical property of the composite material.
3. According to the invention, the aerogel prepared from the nano-fibers and the montmorillonite is added into the polyurethane composite material, and the aerogel can effectively reduce the smoke generation amount in the combustion process of the polyurethane composite material while playing a flame retardant role; and the mechanical property and the heat preservation property of the building material are effectively improved after the corn straws are treated.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a polyurethane composite material for buildings specifically comprises the following steps:
the building material comprises the following components in parts by weight: 20 parts of polyurethane resin, 12 parts of cellulose aerogel, 6 parts of modified montmorillonite, 1 part of dibutyltin dilaurate, 8 parts of corn straw, 6 parts of phenolic resin and 3 parts of ethylenediamine.
The cellulose aerogel is prepared by adopting the following method:
1) Adding cellulose nano-fiber into water, stirring at high speed for 5h to obtain suspension I, adding nano-montmorillonite into water, stirring at high speed to disperse the nano-montmorillonite to obtain suspension II, mixing the suspension I and the suspension II, and stirring for 6h for later use.
2) Freezing the suspension mixed liquor obtained in the step 1) at-50 ℃ for 25min, and then freezing and drying for 45h in a liquid nitrogen environment to obtain the cellulose aerogel.
The modified montmorillonite is prepared by the following method:
the method comprises the following steps: uniformly mixing nano montmorillonite, expanded graphite, aluminum hydroxide and magnesium hydroxide, adding the mixture into distilled water, ultrasonically stirring for 10min, then adding an ammonia water solution to adjust the pH value to 10.5, and stirring for later use, wherein the mass ratio of the nano montmorillonite to the expanded graphite to the aluminum hydroxide to the magnesium hydroxide is 1.
Step two: and (3) moving the mixed solution in the step one to a high-pressure reaction kettle, then placing the mixed solution in an oven, reacting for 5 hours at 210 ℃, cooling, washing with distilled water for three times, and drying at 80 ℃ to obtain the modified montmorillonite.
The preparation method comprises the following steps:
s1: the method comprises the following steps of crushing corn straws into aggregates with different thicknesses of 15mm, adding the aggregates into a sulfuric acid solution, soaking for 2 hours, filtering, washing and drying with water, then adding the aggregates into a mixed solution of water, a nano-silica solution, calcium pyruvate and dimethylformamide, stirring for 3 hours, taking out and drying at 75 ℃ for later use, wherein the mass volume ratio of the water to the nano-silica solution to the calcium pyruvate to the dimethylformamide is 100 mL.
S2: and (2) mixing and stirring the corn straws, the polyurethane resin, the cellulose aerogel, the modified montmorillonite, the dibutyltin dilaurate, the phenolic resin and the ethylenediamine in the step (S1) according to the proportion, wherein the stirring temperature is 80 ℃, the rotating speed is 450rpm/min, and the stirring reaction time is 20min.
S3: pouring the mixture stirred and reacted in the step S2 into a mould, and carrying out three-stage curing molding, wherein the curing temperature of the first stage is 140 ℃, and the curing time is 2 hours; the curing temperature of the second stage is 220 ℃, and the curing time is 2.5h; and the curing temperature of the third stage is 255 ℃, the curing time is 1h, and the polyurethane composite material is obtained after cooling and demolding.
Example 2
A preparation method of a polyurethane composite material for buildings specifically comprises the following steps:
the building material comprises the following components in parts by weight: 30 parts of polyurethane resin, 18 parts of cellulose aerogel, 12 parts of modified montmorillonite, 2 parts of dibutyltin dilaurate, 10 parts of corn straw, 10 parts of phenolic resin and 5 parts of ethylenediamine.
The cellulose aerogel is prepared by adopting the following method:
1) Adding cellulose nano-fiber into water, stirring at high speed for 8h to obtain suspension I, adding nano-montmorillonite into water, stirring at high speed to disperse the nano-montmorillonite to obtain suspension II, mixing the suspension I and the suspension II, and stirring for 9h for later use.
2) Freezing the suspension mixed liquor obtained in the step 1) for 40min at the temperature of-65 ℃, and then freezing and drying for 60h in a liquid nitrogen environment to obtain the cellulose aerogel.
The modified montmorillonite is prepared by the following method:
the method comprises the following steps: uniformly mixing nano montmorillonite, expanded graphite, aluminum hydroxide and magnesium hydroxide, adding the mixture into distilled water, ultrasonically stirring for 15min, then adding an ammonia water solution to adjust the pH value to 11.5, and stirring for later use, wherein the mass ratio of the nano montmorillonite to the expanded graphite to the aluminum hydroxide to the magnesium hydroxide is (2: 0.75).
Step two: and (2) moving the mixed solution in the step one to a high-pressure reaction kettle, then placing the mixed solution in an oven, reacting for 8 hours at 230 ℃, cooling, washing with distilled water for three times, and drying at 90 ℃ to obtain the modified montmorillonite.
The preparation method comprises the following steps:
s1: the method comprises the following steps of crushing corn straws into aggregates with different thicknesses of 30mm, adding the aggregates into a sulfuric acid solution, soaking for 3 hours, filtering, washing with water, drying, adding the aggregates into a mixed solution of water, a nano-silica solution, calcium pyruvate and dimethylformamide, stirring for 5 hours, taking out, and drying at 80 ℃ for later use, wherein the mass-volume ratio of the water to the nano-silica solution to the calcium pyruvate to the dimethylformamide is 150mL.
S2: and (2) mixing and stirring the corn straws, the polyurethane resin, the cellulose aerogel, the modified montmorillonite, the dibutyltin dilaurate, the phenolic resin and the ethylenediamine in the step (S1) according to the proportion, wherein the stirring temperature is 90 ℃, the rotating speed is 600rpm/min, and the stirring reaction time is 40min.
S3: pouring the mixture stirred and reacted in the step S2 into a mold, and carrying out three-stage curing molding, wherein the curing temperature of the first stage is 150 ℃, and the curing time is 3 hours; the curing temperature of the second stage is 230 ℃, and the curing time is 4 hours; and the curing temperature of the third stage is 270 ℃, the curing time is 1.5h, and the polyurethane composite material is obtained after cooling and demolding.
Example 3
A preparation method of a polyurethane composite material for buildings specifically comprises the following steps:
the building material comprises the following components in parts by weight: 25 parts of polyurethane resin, 15 parts of cellulose aerogel, 9 parts of modified montmorillonite, 2 parts of dibutyltin dilaurate, 9 parts of corn straw, 8 parts of phenolic resin and 4 parts of ethylenediamine.
The cellulose aerogel is prepared by adopting the following method:
1) Adding cellulose nano-fiber into water, stirring at high speed for 6h to obtain suspension I, adding nano-montmorillonite into water, stirring at high speed to disperse the nano-montmorillonite to obtain suspension II, mixing the suspension I and the suspension II, and stirring for 7h for later use.
2) Freezing the suspension mixed liquor obtained in the step 1) at-55 ℃ for 30min, and then freezing and drying for 50h in a liquid nitrogen environment to obtain the cellulose aerogel.
The modified montmorillonite is prepared by the following method:
the method comprises the following steps: uniformly mixing nano montmorillonite, expanded graphite, aluminum hydroxide and magnesium hydroxide, adding the mixture into distilled water, ultrasonically stirring for 12min, then adding an ammonia water solution to adjust the pH value to 11, and stirring for later use, wherein the mass ratio of the nano montmorillonite to the expanded graphite to the aluminum hydroxide to the magnesium hydroxide is 1.2.
Step two: and (3) moving the mixed solution in the step one to a high-pressure reaction kettle, then placing the mixed solution in an oven, reacting for 6 hours at 220 ℃, cooling, washing with distilled water for three times, and drying at 85 ℃ to obtain the modified montmorillonite.
The preparation method comprises the following steps:
s1: the method comprises the following steps of crushing corn straws into aggregates with different thicknesses of 20mm, adding the aggregates into a sulfuric acid solution, soaking for 2.5h, filtering, washing with water, drying, adding the aggregates into a mixed solution of water, a nano-silica solution, calcium pyruvate and dimethylformamide, stirring for 4h, taking out, and drying at 77 ℃ for later use, wherein the mass volume ratio of the water, the nano-silica solution, the calcium pyruvate and the dimethylformamide is 1201.8mL.
S2: and (2) mixing and stirring the corn straws, the polyurethane resin, the cellulose aerogel, the modified montmorillonite, the dibutyltin dilaurate, the phenolic resin and the ethylenediamine in the step (S1) according to the proportion, wherein the stirring temperature is 85 ℃, the rotating speed is 500rpm/min, and the stirring reaction time is 25min.
S3: pouring the mixture stirred and reacted in the step S2 into a mold, and carrying out three-stage curing molding, wherein the curing temperature of the first stage is 145 ℃, and the curing time is 2.5 hours; the curing temperature of the second stage is 225 ℃, and the curing time is 3 hours; and the curing temperature of the third stage is 260 ℃, the curing time is 1.2h, and the polyurethane composite material is obtained after cooling and demolding.
Example 4
A preparation method of a polyurethane composite material for buildings specifically comprises the following steps:
the building material comprises the following components in parts by weight: 28 parts of polyurethane resin, 16 parts of cellulose aerogel, 11 parts of modified montmorillonite, 2 parts of dibutyltin dilaurate, 9 parts of corn straw, 9 parts of phenolic resin and 5 parts of ethylenediamine.
The cellulose aerogel is prepared by adopting the following method:
1) Adding cellulose nano-fiber into water, stirring at high speed for 7h to obtain suspension I, adding nano-montmorillonite into water, stirring at high speed to disperse the nano-montmorillonite to obtain suspension II, mixing the suspension I and the suspension II, and stirring for 8h for later use.
2) Freezing the suspension mixed liquor obtained in the step 1) at-60 ℃ for 30min, and then freezing and drying for 55h in a liquid nitrogen environment to obtain the cellulose aerogel.
The modified montmorillonite is prepared by the following method:
the method comprises the following steps: uniformly mixing nano montmorillonite, expanded graphite, aluminum hydroxide and magnesium hydroxide, adding the mixture into distilled water, ultrasonically stirring for 14min, then adding an ammonia water solution to adjust the pH value to 11.2, and stirring for later use, wherein the mass ratio of the nano montmorillonite to the expanded graphite to the aluminum hydroxide to the magnesium hydroxide is 1.8.
Step two: and (2) moving the mixed solution obtained in the step one to a high-pressure reaction kettle, then placing the mixed solution in an oven, reacting for 7 hours at 225 ℃, cooling, washing with distilled water for three times, and drying at 90 ℃ to obtain the modified montmorillonite.
The preparation method comprises the following steps:
s1: the method comprises the following steps of crushing corn straws into aggregates with different thicknesses of 25mm, adding the aggregates into a sulfuric acid solution, soaking for 3 hours, filtering, washing and drying with water, adding the aggregates into a mixed solution of water, a nano-silica solution, calcium pyruvate and dimethylformamide, stirring for 5 hours, taking out, and drying at 79 ℃ for later use, wherein the mass-volume ratio of the water to the nano-silica solution to the calcium pyruvate to the dimethylformamide is 140mL.
S2: and (2) mixing and stirring the corn straws, the polyurethane resin, the cellulose aerogel, the modified montmorillonite, the dibutyltin dilaurate, the phenolic resin and the ethylenediamine in the step (S1) according to the proportion, wherein the stirring temperature is 90 ℃, the rotating speed is 550rpm/min, and the stirring reaction time is 35min.
S3: pouring the mixture stirred and reacted in the step S2 into a mold, and carrying out three-stage curing molding, wherein the curing temperature of the first stage is 150 ℃, and the curing time is 3 hours; the curing temperature of the second stage is 230 ℃, and the curing time is 3h; and the curing temperature of the third stage is 265 ℃, the curing time is 1.2h, and the polyurethane composite material is obtained after cooling and demolding.
Examples of the experiments
Performance test 1-mechanical property testing: the mechanical properties of the building materials prepared in examples 1 to 4 were measured according to GB T/2567-2008, and the results are shown in Table 1,
table 1. Mechanical properties test results:
as can be seen from Table 1, the polyurethane composite materials prepared in examples 1-4 of the present invention have tensile strength of 41MPa or more, impact strength of 385N or more, elongation at break of 45.25% or more, and excellent mechanical properties and flexibility.
Performance test 2-flame retardant performance test: the building materials prepared in examples 1 to 4 were subjected to limit epoxy index, maximum smoke density and combustion grade tests, the test results of which are shown in table 2,
table 2. Flame retardant properties test results:
as can be seen from Table 2, the limiting epoxy index of the polyurethane composite materials prepared in examples 1-4 is above 38.4, and the maximum smoke density is about 37.3, which shows that the polyurethane composite materials of the invention have lower smoke generation amount, and the flame retardant grades are V-0 grade through a vertical combustion test, so that the polyurethane composite materials have excellent flame retardant property, and meanwhile, the thermal conductivity is about 0.023W/K.m, which shows that the polyurethane composite materials of the invention have excellent heat insulation property.
Claims (2)
1. The preparation method of the polyurethane composite material for the building is characterized in that the building material comprises the following components in parts by weight: 20-30 parts of polyurethane resin, 12-18 parts of cellulose aerogel, 6-12 parts of modified montmorillonite, 1-2 parts of dibutyltin dilaurate, 8-10 parts of corn straws, 6-10 parts of phenolic resin and 3-5 parts of ethylenediamine;
the preparation method comprises the following steps:
s1: crushing corn straws into aggregates with different thicknesses of 15-30 mm, adding the aggregates into a sulfuric acid solution, soaking for 2-3 h, filtering, washing with water, drying, adding the aggregates into a mixed solution of water, a nano-silica solution, calcium pyruvate and dimethylformamide, stirring for 3-5 h, taking out, and drying at 75-80 ℃ for later use;
s2: mixing and stirring the corn straws, the polyurethane resin, the cellulose aerogel, the modified montmorillonite, the dibutyltin dilaurate, the phenolic resin and the ethylenediamine in the step S1 according to the proportion, wherein the stirring temperature is 80-90 ℃, the rotating speed is 450-600 rpm/min, and the stirring reaction time is 20-40 min;
s3: pouring the mixture stirred and reacted in the step S2 into a mold, curing and molding, and cooling and demolding to obtain the polyurethane composite material;
the cellulose aerogel is prepared by adopting the following method:
1) Adding cellulose nano-fiber into water, stirring at a high speed for 5-8 h to obtain a suspension I, adding nano-montmorillonite into water, stirring at a high speed to disperse the nano-montmorillonite to obtain a suspension II, mixing the suspension I and the suspension II, and stirring for 6-9 h for later use;
2) Freezing the suspension mixed solution obtained in the step 1) for 25-40 min at the temperature of-50 to-65 ℃, and then freezing and drying for 45-60 h in a liquid nitrogen environment to obtain cellulose aerogel;
the modified montmorillonite is prepared by the following method:
the method comprises the following steps: uniformly mixing nano montmorillonite, expanded graphite, aluminum hydroxide and magnesium hydroxide, adding the mixture into distilled water, ultrasonically stirring the mixture for 10 to 15min, then adding an ammonia water solution to adjust the pH value to 10.5 to 11.5, and stirring the mixture for later use;
step two: transferring the mixed solution in the step one to a high-pressure reaction kettle, then placing the mixed solution in an oven, reacting for 5-8 h at 210-230 ℃, cooling, washing with distilled water for three times, and drying at 80-90 ℃ to obtain the modified montmorillonite;
wherein the mass ratio of the nano montmorillonite, the expanded graphite, the aluminum hydroxide and the magnesium hydroxide is (1-2) to (0.4-0.75) to (0.42-0.78) to (0.36-0.69); the mass volume ratio of the water, the nano-silica solution, the calcium pyruvate and the dimethylformamide is (100-150) mL, (4.2-6.8) mL, (1.3-1.9) g and (10-16) mL.
2. The method for preparing a polyurethane composite material used in construction according to claim 1, wherein the curing molding in step S3 is divided into three stages, the curing temperature of the first stage is 140 to 150 ℃, and the curing time is 2 to 3 hours; the curing temperature of the second stage is 220-230 ℃, and the curing time is 2.5-4 h; the curing temperature of the third stage is 255-270 ℃, and the curing time is 1-1.5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111058444.7A CN113583429B (en) | 2021-09-10 | 2021-09-10 | Preparation method of polyurethane composite material for building |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111058444.7A CN113583429B (en) | 2021-09-10 | 2021-09-10 | Preparation method of polyurethane composite material for building |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113583429A CN113583429A (en) | 2021-11-02 |
| CN113583429B true CN113583429B (en) | 2022-10-14 |
Family
ID=78241701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111058444.7A Active CN113583429B (en) | 2021-09-10 | 2021-09-10 | Preparation method of polyurethane composite material for building |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113583429B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116790113A (en) * | 2023-08-01 | 2023-09-22 | 山西百澳幕墙装饰有限公司 | Polyurethane flame-retardant heat-insulating material, heat-insulating aluminum alloy and preparation method of heat-insulating aluminum alloy |
| CN119081441B (en) * | 2024-11-01 | 2025-03-18 | 河北金坤工程材料有限公司 | A quick-repair expansion joint polyurethane elastomer composition and preparation method thereof |
| CN120757327B (en) * | 2025-09-08 | 2025-11-11 | 江苏荣兴亚克力建装材料有限公司 | A straw aerogel composite insulation board and its preparation method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1832951B (en) * | 2003-06-09 | 2011-08-03 | 大八化学工业株式会社 | Organophosphorus compound having phosphate-phosphonate bond, flame-retardant fiber and composition using same |
| CN1323118C (en) * | 2005-07-27 | 2007-06-27 | 厦门大学 | Tunnel fireproof coating modifier based on polymer/clay intercalation modification technology and preparation method thereof |
| CN103790248B (en) * | 2014-01-27 | 2016-08-17 | 钟春燕 | A kind of preparation method of thermal-insulation heat-resistant plate for building |
| CN103768752B (en) * | 2014-02-20 | 2015-07-08 | 铜陵祥云消防科技有限责任公司 | Dry powder extinguisher containing modified smectite powder |
| CN106832635A (en) * | 2016-12-30 | 2017-06-13 | 安徽华普环境修复材料科技有限公司 | A kind of fire-retardant heat insulation composite sandwich plate |
| CN108410014A (en) * | 2018-01-15 | 2018-08-17 | 大连亚泰科技新材料股份有限公司 | A kind of montmorillonite/magnesium hydroxide composite flame retardant material and preparation method |
| CN108483996A (en) * | 2018-04-09 | 2018-09-04 | 合肥聪亨新型建材科技有限公司 | A kind of corrosion-resistant thermal insulation material of construction wall and preparation method thereof |
| CN108866815A (en) * | 2018-08-02 | 2018-11-23 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of coral fleece sqouynd absorption lowering noise textile material |
| CN111440353A (en) * | 2020-04-26 | 2020-07-24 | 云南中烟工业有限责任公司 | Preparation method of heat-conducting hydrophobic flame-retardant nano-cellulose aerogel |
-
2021
- 2021-09-10 CN CN202111058444.7A patent/CN113583429B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113583429A (en) | 2021-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113583429B (en) | Preparation method of polyurethane composite material for building | |
| CN105440657B (en) | External wall thermal insulation material and preparation method thereof | |
| CN101717514B (en) | Modified phenolic resin, foamed material thereof and method for preparing same | |
| CN102775766B (en) | Flame-retardant rigid polyurethane foaming plastic composite material and preparation method thereof | |
| CN101307129B (en) | Polyurethane/organic montmorillonite nano composite material and method for preparing same | |
| CN104387608A (en) | Self-flame-retardant modified melamine-formaldehyde foam as well as preparation method and application thereof | |
| CN102040364A (en) | Water-resistant vermiculite insulation board and preparation method thereof | |
| CN114835942A (en) | High-strength sodium alginate/lignin flame-retardant aerogel and preparation method and application thereof | |
| CN103304260A (en) | Foamed concrete heat preservation plate and preparation method thereof | |
| CN111348883A (en) | Autoclaved aerated concrete with high crack resistance and low water absorption rate and preparation method thereof | |
| CN110105683B (en) | Polystyrene foam material and preparation method thereof | |
| CN107556514B (en) | Preparation method of modified melamine formaldehyde rigid foam board for flame retardation and heat preservation | |
| CN115651150A (en) | Water glass filled modified flame-retardant polyurethane foam and preparation method thereof | |
| CN106916275A (en) | A kind of composite modified polyurethane type foam plastics and preparation method thereof | |
| CN113248206A (en) | Cement-based polyurethane composite insulation board and preparation method thereof | |
| CN105153395B (en) | A kind of polymerization ceramic material and preparation method thereof | |
| CN118325030A (en) | Sound-insulation heat-insulation polyurethane composite board | |
| CN109836767A (en) | A kind of high-performance modified phenolic resin cold-storage insulation board | |
| CN116444914A (en) | Low thermal conductivity rigid cross-linked polyvinyl chloride foam and preparation method thereof | |
| CN104845356A (en) | Halogen-free flame-retardant rigid polyurethane foam material and preparation method thereof | |
| CN116554614A (en) | Preparation method of flame-retardant heat-insulating PVC/rice hull ash-based aerogel composite board | |
| CN113444327A (en) | Preparation method of borosilicate flame-retardant wall insulation board | |
| CN114956863A (en) | Building external wall heat-insulation composite board and processing technology thereof | |
| CN117986760B (en) | Flame-retardant polystyrene board and preparation method thereof | |
| CN107325423A (en) | A kind of energy-saving floor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220913 Address after: 255000 north of Nanling South Road, high tech Zone, Zibo City, Shandong Province, east of Zidong Railway Applicant after: Shandong century United New Material Technology Co.,Ltd. Address before: 310000 no.5000, Jiangdong 1st Road, Qianjin Street, Qiantang New District, Hangzhou City, Zhejiang Province Applicant before: Hangzhou Dili New Material Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |