CN116948390B - Composite heat-insulating material based on aluminum silicate fibers - Google Patents

Composite heat-insulating material based on aluminum silicate fibers Download PDF

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CN116948390B
CN116948390B CN202311225247.9A CN202311225247A CN116948390B CN 116948390 B CN116948390 B CN 116948390B CN 202311225247 A CN202311225247 A CN 202311225247A CN 116948390 B CN116948390 B CN 116948390B
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aluminum silicate
stirring
parts
silicate fiber
flame retardant
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CN116948390A (en
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秦伯军
谢存剑
张君
秦天德
吉娇
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Yingsheng Energy Saving Group Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009Use of pretreated compounding ingredients
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141Hydrocarbons
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/02CO2-releasing, e.g. NaHCO3 and citric acid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/04Starch derivatives
    • C08J2403/06Esters

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Abstract

The invention relates to the technical field of materials, and discloses a composite thermal insulation material based on aluminum silicate fibers, which is prepared from polyether polyol, a surfactant, a crosslinked starch intumescent flame retardant, a foaming agent A, a foaming agent B, polyisocyanate, aluminum silicate fiber aerogel and an organotin catalyst.

Description

Composite heat-insulating material based on aluminum silicate fibers
Technical Field
The invention relates to the technical field of materials, in particular to a composite heat-insulating material based on aluminum silicate fibers.
Background
In modern buildings, indoor heat preservation effect is paid more attention, and heat loss is relatively large due to poor heat preservation effect of a wall structure in building energy consumption, so that a heat preservation layer is enclosed on the outer side of a wall, and the heat preservation layer gradually becomes a main stream method for realizing heat preservation of the building, so that research on heat preservation materials is increased. The heat insulating material mainly comprises inorganic heat insulating materials and organic heat insulating materials, wherein the inorganic heat insulating materials mainly comprise vitrified microbeads, rock wool and the like, and the inorganic heat insulating materials have the defects of difficult construction, poor waterproof effect and the like although the heat conducting coefficient of the inorganic heat insulating materials is low, so that the inorganic heat insulating materials are not suitable for being used as heat insulating materials of building outer walls. The organic heat-insulating material is mainly foam heat-insulating material, and among various organic heat-insulating materials, the polyurethane foam heat-insulating material has the advantages of strong heat resistance, ageing resistance, good waterproof performance and the like, so that the polyurethane foam heat-insulating material is greatly popularized in the building energy-saving field. However, the polyurethane heat-insulating material has poor flame retardant property and restricts further development, so that the polyurethane heat-insulating material has important significance in flame retardant modification.
The invention patent with application number of CN201310510247.3 discloses a flame-retardant heat-insulating rigid polyurethane foam material, which improves the flame retardant property of the polyurethane foam material by utilizing the physical flame retardant effect of the modified attapulgite, but from the test result, the oxygen index of the polyurethane foam is only 25, and the polyurethane foam still shows inflammable property, so that the polyurethane foam is difficult to effectively flame-retardant modify by utilizing inorganic materials.
Based on the above, the invention provides the polyurethane foam composite heat-insulating material, and the prepared polyurethane foam composite heat-insulating material has good heat preservation and flame retardance effects by adding the crosslinked starch intumescent flame retardant and the aluminum silicate fiber aerogel at the same time, and can be directly used as a heat-insulating material for an outer wall of a building.
Disclosure of Invention
The invention aims to provide a composite heat-insulating material based on aluminum silicate fibers, which solves the problem of poor flame retardant property of polyurethane composite heat-insulating materials.
The aim of the invention can be achieved by the following technical scheme:
the composite heat-insulating material based on the aluminum silicate fiber is prepared from the following raw materials in parts by weight: 80-90 parts of polyether polyol, 4-6 parts of surfactant, 4-8 parts of crosslinked starch intumescent flame retardant, 1-2 parts of foaming agent A, 5-10 parts of foaming agent B, 70-85 parts of polyisocyanate, 1-3 parts of aluminum silicate fiber aerogel and 0.5-1 part of organotin catalyst;
the crosslinked starch intumescent flame retardant has a crosslinked structure, and the structure contains a nitrogen-phosphorus flame retardant.
Further, the polyether polyol is any one of polyether polyol 4110 or polyether polyol 403; the surfactant is AK-158; the foaming agent A is purified water; the foaming agent B is any one of n-hexane or cyclopentane; the polyisocyanate is isocyanate PM-200; the organic tin catalyst is any one of stannous octoate or dibutyl tin dilaurate.
Further, the preparation method of the crosslinked starch intumescent flame retardant comprises the following steps:
step S1: stirring and mixing starch and N, N-dimethylformamide to form uniform dispersion liquid, adding 5-isocyanate isophthaloyl chloride and a catalyst into the dispersion liquid, introducing nitrogen for protection after the addition, stirring at room temperature for 6-8 hours, and filtering out solid materials to obtain a crosslinked starch intermediate;
step S2: stirring and mixing the crosslinked starch intermediate with dimethyl sulfoxide, adding a phosphorus-containing monomer and triethylamine, uniformly mixing, placing the mixture at 90-100 ℃, stirring for 8-12h, cooling and discharging, and filtering to obtain the crosslinked starch intumescent flame retardant.
Further, in step S1, the catalyst is pyridine.
Further, in step S2, the phosphorus-containing monomer is any one of dimethyl phosphite, diethyl phosphite or dibenzyl phosphite.
In the technical scheme, the starch structure contains hydroxyl, and can be subjected to esterification condensation reaction with acyl chloride groups in a 5-isocyanate isophthaloyl chloride structure at room temperature to crosslink starch, so that a crosslinked starch intermediate containing active isocyanate groups in the structure is prepared, the isocyanate groups in the structure can be subjected to reaction with P-H in a phosphorus-containing monomer structure at high temperature, and a nitrogen-phosphorus flame retardant is introduced into the starch structure to form the crosslinked starch intumescent flame retardant taking crosslinked starch as a carbon source and nitrogen-phosphorus flame retardant as an air source and an acid source.
Further, the preparation method of the aluminum silicate fiber aerogel comprises the following steps:
step SS1: pretreating aluminum silicate fibers, mixing the pretreated aluminum silicate fibers with a mixed solution of ethanol and purified water in a volume ratio of 3:1, performing ultrasonic dispersion to form uniform dispersion, adding 3- (methacryloyloxy) propyl trimethoxy silane, heating to 60-70 ℃ after the addition, stirring for 4-8 hours, cooling and discharging, and centrifuging to separate solid materials to obtain modified aluminum silicate fibers;
step SS2: uniformly dispersing modified aluminum silicate fibers in a mixed solution of ethanol and purified water in a volume ratio of 1:1, adding hydroxyethyl methacrylate, N-methylene acrylamide and an initiator, stirring uniformly, carrying out heat preservation at 80-85 ℃ and stirring for 18-24 hours, and separating out solid materials to obtain a precursor;
step SS3: dispersing the precursor in purified water, adding an emulsifying agent, uniformly mixing, continuously adding cyclohexane, stirring uniformly to form stable emulsion, stirring and emulsifying at 50-60 ℃ for 20-40min, adding an initiating agent, heating to 70-80 ℃ after the addition, stirring for 6-8h, separating out materials, and washing and freeze-drying to obtain the aluminum silicate fiber aerogel.
Further, in step SS1, the pretreatment method of the aluminum silicate fiber specifically includes: soaking aluminum silicate fibers in a sodium carbonate solution with the mass fraction of 1-2%, centrifuging out materials after 2-4 hours, and carrying out washing and vacuum drying processes.
Further, in step SS2 and step SS3, the initiator is any one of benzoyl peroxide or dicumyl peroxide.
Further, in step SS3, the emulsifier is sodium dodecyl sulfate.
In the technical scheme, a possible mechanism is that a silane coupling agent is used for modifying the treated aluminum silicate fiber to form a modified aluminum silicate fiber, unsaturated alkenyl functional groups in a silane coupling agent structure are used as active initiation sites, hydroxyethyl methacrylate and N, N-methylene acrylamide are initiated to carry out cross-linking polymerization, so that macromolecular chains are loaded on the surface of the aluminum silicate fiber, the macromolecular chains are used as cross-linking points, the aluminum silicate fibers are mutually connected under the action of Pickering emulsion, and then the two-dimensional aluminum silicate fiber is constructed into an aerogel structure with a three-dimensional network structure, so that the aluminum silicate fiber aerogel is prepared.
Further, the preparation method of the composite heat insulation material comprises the following steps:
step one: vacuum dehydrating polyether polyol, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant and a crosslinked starch intumescent flame retardant, stirring and mixing for 10-20min at a rotating speed of 500-1000r/min, adding a foaming agent A, and continuously stirring for 5-10min to form uniform premix;
step two: adding a foaming agent B into the premix, adjusting the rotating speed to 1000-1500r/min, stirring and mixing for 1-2min, then adding polyisocyanate, aluminum silicate fiber aerogel and an organotin catalyst, stirring and mixing uniformly, pouring into a mould, standing and foaming for 20-30min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 60-70 ℃ for curing for 12-18h to obtain the composite heat-insulating material.
The invention has the beneficial effects that:
1) According to the invention, the crosslinked starch intumescent flame retardant is prepared to carry out flame retardant modification on the polyurethane foam composite heat insulation material, and the starch with a crosslinked structure has higher char yield, so that when combustion occurs, the crosslinked starch intumescent flame retardant can enable the surface of the composite heat insulation material to quickly form a very compact expanded carbon layer structure, oxygen and heat can be well isolated, combustion is difficult to continuously carry out, and the flame retardant property of the composite heat insulation material is effectively improved.
2) According to the invention, the two-dimensional aluminum silicate fiber is constructed into the aluminum silicate fiber aerogel with a three-dimensional network structure, and as the surface of the aluminum silicate fiber aerogel can form a polymer molecular chain containing hydroxyl groups in the preparation process of the aluminum silicate fiber aerogel, the polymer molecular chain can participate in the reaction in the preparation process of the polyurethane foam heat insulation material, and can be uniformly dispersed in a composite heat insulation material matrix, and the aluminum silicate fiber aerogel exists in the form of cross-linked core points to generate a skeleton supporting effect, so that the mechanical property of the composite heat insulation material can be enhanced. In addition, the aluminum silicate fiber aerogel has a unique three-dimensional air hole structure, and can form a barrier effect in the composite heat insulation material by utilizing the air hole structure, so that the heat transfer is reduced, the heat conductivity coefficient of the composite heat insulation material is further reduced, and the composite heat insulation material has a better heat insulation effect. Meanwhile, the uniformly dispersed aluminum silicate fiber aerogel can also form a stable protective layer, and the stable protective layer cooperates with the crosslinked starch intumescent flame retardant to improve the flame retardant property of the composite heat insulation material.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a crosslinked starch intumescent flame retardant of the invention;
FIG. 2 is a scanning electron microscope image of an aluminum silicate fiber aerogel of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The crosslinked starch intumescent flame retardants used in the following examples and comparative examples were prepared by the following methods:
step S1: 3.5g of starch and N, N-dimethylformamide are stirred and mixed to form a uniform dispersion, 2.5g of 5-isocyanate isophthaloyl chloride and 0.2g of pyridine are added into the dispersion, nitrogen is introduced for protection after the addition, and after stirring for 8 hours at room temperature, solid materials are filtered out to obtain a crosslinked starch intermediate;
step S2: 3g of crosslinked starch intermediate and dimethyl sulfoxide are stirred and mixed, 1.2g of diethyl phosphite and 0.5g of triethylamine are added, after the mixture is uniformly mixed, the mixture is placed in the temperature of 95 ℃, after stirring for 9 hours, the temperature is reduced, the material is discharged, and the crosslinked starch intumescent flame retardant is obtained through filtration.
The crosslinked starch intumescent flame retardant was infrared characterized using the potassium bromide tabletting method, the results are shown in FIG. 1, wherein 3312cm -1 Is a hydroxyl telescopic vibration peak of 3294cm -1 Is an N-H telescopic vibration peak, 3000-3100 cm -1 Is C-H telescopic vibration peak in benzene ring, 1751cm -1 For C=O stretching vibration peak in ester group, 1646cm -1 As C=O stretching vibration peak in amide group 1472cm -1 Is P-C characteristic absorption peak, 1244cm -1 Characteristic absorption peak for p=o.
The aluminum silicate fiber aerogels used in the following examples and comparative examples were prepared by the following methods:
step SS1, soaking 5g of aluminum silicate fiber in a sodium carbonate solution with the mass fraction of 1.5%, centrifuging out materials after 3 hours, and obtaining pretreated aluminum silicate fiber through washing and vacuum drying processes;
step SS2: mixing 3.2g of pretreated aluminum silicate fiber with a mixed solution of ethanol and purified water in a volume ratio of 3:1, performing ultrasonic dispersion to form uniform dispersion, adding 5g of 3- (methacryloyloxy) propyl trimethoxysilane, heating to 65 ℃ after the addition, stirring for 6 hours, cooling, discharging, and centrifuging to separate solid materials to obtain modified aluminum silicate fiber;
step SS3: 3g of modified aluminum silicate fiber and ethanol and purified water with the volume ratio of 1:1 are mixed and uniformly dispersed, 6.5g of hydroxyethyl methacrylate, 0.2g of N, N-methylene acrylamide and 0.01g of benzoyl peroxide are added and stirred uniformly, and after the mixture is kept at 80 ℃ and stirred for 24 hours, solid materials are separated out, and a precursor is obtained;
step SS4: dispersing 2g of precursor in purified water, adding 1g of sodium dodecyl sulfate, uniformly mixing, continuously adding cyclohexane, uniformly stirring to form stable emulsion, stirring and emulsifying at 55 ℃ for 30min, adding 0.5g of benzoyl peroxide, heating to 75 ℃ after the addition, stirring for 8h, separating out materials, and washing and freeze-drying to obtain the aluminum silicate fiber aerogel.
The aluminum silicate fiber aerogel is subjected to morphological analysis by using a Hitachi S-4800 scanning electron microscope, the test result is shown in fig. 2, and as can be observed from fig. 2, the aluminum silicate fiber aerogel is formed by mutually connecting aluminum silicate fibers, is in a three-dimensional network shape and is rich in pore structures.
Example 1
The composite heat-insulating material based on the aluminum silicate fiber is prepared from the following raw materials in parts by weight: 4110 80 parts of polyether polyol, 4 parts of surfactant AK-158 parts of crosslinked starch intumescent flame retardant, 1 part of purified water, 5 parts of normal hexane, 200 parts of isocyanate PM-200 parts, 1 part of aluminum silicate fiber aerogel and 0.5 part of stannous octoate;
the preparation method of the composite heat-insulating material comprises the following steps:
step one: after vacuum dehydration of polyether polyol 4110, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant and a crosslinked starch intumescent flame retardant, stirring and mixing for 20min at a rotating speed of 500r/min, adding purified water, and continuously stirring for 10min to form a uniform premix;
step two: adding n-hexane into the premix, adjusting the rotating speed to 1000r/min, stirring and mixing for 2min, adding isocyanate PM-200, aluminum silicate fiber aerogel and stannous octoate, stirring and mixing uniformly, pouring into a mould, standing and foaming for 20min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 60 ℃ for curing for 12 hours to obtain the composite heat-insulating material.
Example 2
The composite heat-insulating material based on the aluminum silicate fiber is prepared from the following raw materials in parts by weight: 4110 85 parts of polyether polyol, 5 parts of surfactant AK-158 parts of cross-linked starch intumescent flame retardant, 7 parts of purified water, 8 parts of cyclopentane, 200-75 parts of isocyanate PM, 2 parts of aluminum silicate fiber aerogel and 0.6 part of dibutyltin dilaurate;
the preparation method of the composite heat-insulating material comprises the following steps:
step one: after vacuum dehydration of polyether polyol 4110, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant and a crosslinked starch intumescent flame retardant, stirring and mixing for 15min at a rotating speed of 800r/min, adding purified water, and continuously stirring for 10min to form a uniform premix;
step two: adding cyclopentane into the premix, adjusting the rotating speed to 1500r/min, stirring and mixing for 1min, then adding isocyanate PM-200, aluminum silicate fiber aerogel and dibutyltin dilaurate, stirring and mixing uniformly, pouring into a mould, standing and foaming for 25min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 65 ℃ for curing for 16 hours to obtain the composite heat-insulating material.
Example 3
The composite heat-insulating material based on the aluminum silicate fiber is prepared from the following raw materials in parts by weight: 4110 90 parts of polyether polyol, 6 parts of surfactant AK-158 parts of cross-linked starch intumescent flame retardant, 8 parts of purified water, 10 parts of normal hexane, 200 parts of isocyanate PM-200, 3 parts of aluminum silicate fiber aerogel and 1 part of stannous octoate;
the preparation method of the composite heat-insulating material comprises the following steps:
step one: after vacuum dehydration of polyether polyol 4110, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant and a crosslinked starch intumescent flame retardant, stirring and mixing for 10min at a rotating speed of 1000r/min, adding purified water, and continuing stirring for 5min to form a uniform premix;
step two: adding n-hexane into the premix, adjusting the rotating speed to 1500r/min, stirring and mixing for 1min, adding isocyanate PM-200, aluminum silicate fiber aerogel and stannous octoate, stirring and mixing uniformly, pouring into a mould, standing and foaming for 30min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 70 ℃ for curing for 18 hours to obtain the composite heat-insulating material.
Comparative example 1
The composite heat-insulating material is prepared from the following raw materials in parts by weight: 4110 85 parts of polyether polyol, 5 parts of surfactant AK-158 parts of cross-linked starch intumescent flame retardant, 7 parts of purified water, 8 parts of cyclopentane, 75 parts of isocyanate PM-200 and 0.6 part of dibutyltin dilaurate;
the preparation method of the composite heat-insulating material comprises the following steps:
step one: after vacuum dehydration of polyether polyol 4110, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant and a crosslinked starch intumescent flame retardant, stirring and mixing for 15min at a rotating speed of 800r/min, adding purified water, and continuously stirring for 10min to form a uniform premix;
step two: adding cyclopentane into the premix, adjusting the rotating speed to 1500r/min, stirring and mixing for 1min, adding isocyanate PM-200 and dibutyltin dilaurate, stirring and mixing uniformly, pouring into a mould, standing and foaming for 25min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 65 ℃ for curing for 16 hours to obtain the composite heat-insulating material.
Comparative example 2
The composite heat-insulating material is prepared from the following raw materials in parts by weight: 4110 85 parts of polyether polyol, 5 parts of surfactant AK-158 parts of cross-linked starch intumescent flame retardant, 7 parts of purified water, 8 parts of cyclopentane, 200-75 parts of isocyanate PM, 2 parts of aluminum silicate fiber and 0.6 part of dibutyltin dilaurate;
the preparation method of the composite heat-insulating material comprises the following steps:
step one: after vacuum dehydration of polyether polyol 4110, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant and a crosslinked starch intumescent flame retardant, stirring and mixing for 15min at a rotating speed of 800r/min, adding purified water, and continuously stirring for 10min to form a uniform premix;
step two: adding cyclopentane into the premix, adjusting the rotating speed to 1500r/min, stirring and mixing for 1min, adding isocyanate PM-200, aluminum silicate fiber and dibutyltin dilaurate, stirring and mixing uniformly, pouring into a mould, standing and foaming for 25min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 65 ℃ for curing for 16 hours to obtain the composite heat-insulating material.
Comparative example 3
The composite heat-insulating material is prepared from the following raw materials in parts by weight: 4110 85 parts of polyether polyol, 5 parts of surfactant AK-158 parts of purified water, 8 parts of cyclopentane, 2 parts of polyisocyanate PM-200 75 parts of aluminum silicate fiber aerogel and 0.6 part of dibutyltin dilaurate;
the preparation method of the composite heat-insulating material comprises the following steps:
step one: after vacuum dehydration of polyether polyol 4110, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant, stirring and mixing for 15min at a rotating speed of 800r/min, adding purified water, and continuously stirring for 10min to form a uniform premix;
step two: adding cyclopentane into the premix, adjusting the rotating speed to 1500r/min, stirring and mixing for 1min, then adding polyisocyanate PM-200, aluminum silicate fiber aerogel and dibutyltin dilaurate, stirring and mixing uniformly, pouring into a mould, standing and foaming for 25min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 65 ℃ for curing for 16 hours to obtain the composite heat-insulating material.
Comparative example 4
The composite heat-insulating material is prepared from the following raw materials in parts by weight: 4110 85 parts of polyether polyol, 5 parts of surfactant AK-158 parts, 2 parts of purified water, 8 parts of cyclopentane, 75 parts of isocyanate PM-200 parts and 0.6 part of dibutyltin dilaurate;
the preparation method of the composite heat-insulating material comprises the following steps:
step one: after vacuum dehydration of polyether polyol 4110, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant, stirring and mixing for 15min at a rotating speed of 800r/min, adding purified water, and continuously stirring for 10min to form a uniform premix;
step two: adding cyclopentane into the premix, adjusting the rotating speed to 1500r/min, stirring and mixing for 1min, adding isocyanate PM-200 and dibutyltin dilaurate, stirring and mixing uniformly, pouring into a mould, standing and foaming for 25min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 65 ℃ for curing for 16 hours to obtain the composite heat-insulating material.
The following performance tests were carried out on the composite insulation materials prepared in examples 1 to 3 and comparative examples 1 to 4 according to the present invention:
performing limiting oxygen index test by referring to standard GB/T2406.2-2009;
performing flame retardant grade test by referring to a standard GB/T2408-2021;
performing compression performance test by referring to standard GB/T8813-2020;
the heat conductivity coefficient is tested by referring to the standard GB/T3399-1982;
the test results are recorded in the following table:
as shown by test results in the table, the composite heat insulation material prepared in the embodiment 1-3 has good flame retardant property, excellent mechanical property, low heat conductivity coefficient and good heat insulation effect.
The composite thermal insulation material prepared in comparative example 1 has good flame retardant performance, but the mechanical properties and thermal insulation effects are general, and the aluminum silicate fibers are added in the composite thermal insulation material prepared in comparative example 2, so that various performances are improved compared with the composite thermal insulation material prepared in comparative example 1, because the aluminum silicate fibers are fireproof materials and have higher mechanical strength and lower thermal conductivity, various performances of the composite thermal insulation material can be improved to a certain extent.
The composite thermal insulation material prepared in comparative example 3 has no crosslinked starch intumescent flame retardant added, so the flame retardant performance is poor.
The composite thermal insulation material prepared in comparative example 4 is free of aluminum silicate fiber aerogel and crosslinked starch intumescent flame retardant, so that all performances are the worst.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (7)

1. The composite heat-insulating material based on the aluminum silicate fiber is characterized by being prepared from the following raw materials in parts by weight: 80-90 parts of polyether polyol, 4-6 parts of surfactant, 4-8 parts of crosslinked starch intumescent flame retardant, 1-2 parts of foaming agent A, 5-10 parts of foaming agent B, 70-85 parts of polyisocyanate, 1-3 parts of aluminum silicate fiber aerogel and 0.5-1 part of organotin catalyst;
the crosslinked starch intumescent flame retardant has a crosslinked structure, and the structure contains a nitrogen-phosphorus flame retardant;
the preparation method of the crosslinked starch intumescent flame retardant comprises the following steps:
step S1: stirring and mixing starch and N, N-dimethylformamide to form uniform dispersion liquid, adding 5-isocyanate isophthaloyl chloride and a catalyst into the dispersion liquid, introducing nitrogen for protection after the addition, stirring at room temperature for 6-8 hours, and filtering out solid materials to obtain a crosslinked starch intermediate;
step S2: stirring and mixing the crosslinked starch intermediate with dimethyl sulfoxide, adding a phosphorus-containing monomer and triethylamine, uniformly mixing, placing the mixture in a temperature of 90-100 ℃, stirring for 8-12h, cooling and discharging, and filtering to obtain the crosslinked starch intumescent flame retardant;
the phosphorus-containing monomer is any one of dimethyl phosphite, diethyl phosphite or dibenzyl phosphite;
the preparation method of the aluminum silicate fiber aerogel comprises the following steps:
step SS1: pretreating aluminum silicate fibers, mixing the pretreated aluminum silicate fibers with a mixed solution of ethanol and purified water in a volume ratio of 3:1, performing ultrasonic dispersion to form uniform dispersion, adding 3- (methacryloyloxy) propyl trimethoxy silane, heating to 60-70 ℃ after the addition, stirring for 4-8 hours, cooling and discharging, and centrifuging to separate solid materials to obtain modified aluminum silicate fibers;
step SS2: uniformly dispersing modified aluminum silicate fibers in a mixed solution of ethanol and purified water in a volume ratio of 1:1, adding hydroxyethyl methacrylate, N-methylene acrylamide and an initiator, stirring uniformly, carrying out heat preservation at 80-85 ℃ and stirring for 18-24 hours, and separating out solid materials to obtain a precursor;
step SS3: dispersing the precursor in purified water, adding an emulsifying agent, uniformly mixing, continuously adding cyclohexane, stirring uniformly to form stable emulsion, stirring and emulsifying at 50-60 ℃ for 20-40min, adding an initiating agent, heating to 70-80 ℃ after the addition, stirring for 6-8h, separating out materials, and washing and freeze-drying to obtain the aluminum silicate fiber aerogel.
2. The aluminum silicate fiber-based composite thermal insulation material according to claim 1, wherein the polyether polyol is any one of polyether polyol 4110 or polyether polyol 403; the surfactant is AK-158; the foaming agent A is purified water; the foaming agent B is any one of n-hexane or cyclopentane; the polyisocyanate is isocyanate PM-200; the organic tin catalyst is any one of stannous octoate or dibutyl tin dilaurate.
3. The composite thermal insulation material based on aluminum silicate fiber according to claim 1, wherein in step S1, the catalyst is pyridine.
4. The composite thermal insulation material based on aluminum silicate fiber according to claim 1, wherein in step SS1, the pretreatment method of the aluminum silicate fiber specifically comprises: soaking aluminum silicate fibers in a sodium carbonate solution with the mass fraction of 1-2%, centrifuging out materials after 2-4 hours, and carrying out washing and vacuum drying processes.
5. The composite thermal insulation material based on aluminum silicate fiber according to claim 1, wherein in the step SS2 and the step SS3, the initiator is any one of benzoyl peroxide or dicumyl peroxide.
6. The composite insulation material based on aluminum silicate fiber according to claim 1, wherein in step SS3, the emulsifier is sodium dodecyl sulfate.
7. The composite thermal insulation material based on aluminum silicate fiber according to claim 1, wherein the preparation method of the composite thermal insulation material comprises the following steps:
step one: vacuum dehydrating polyether polyol, pouring the dehydrated polyether polyol into a stirring kettle, adding a surfactant and a crosslinked starch intumescent flame retardant, stirring and mixing for 10-20min at a rotating speed of 500-1000r/min, adding a foaming agent A, and continuously stirring for 5-10min to form uniform premix;
step two: adding a foaming agent B into the premix, adjusting the rotating speed to 1000-1500r/min, stirring and mixing for 1-2min, then adding polyisocyanate, aluminum silicate fiber aerogel and an organotin catalyst, stirring and mixing uniformly, pouring into a mould, standing and foaming for 20-30min to obtain a foaming material;
step three: and (3) placing the foaming material in a temperature environment of 60-70 ℃ for curing for 12-18h to obtain the composite heat-insulating material.
CN202311225247.9A 2023-09-21 2023-09-21 Composite heat-insulating material based on aluminum silicate fibers Active CN116948390B (en)

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CN115403609A (en) * 2022-05-09 2022-11-29 江苏瑞洋安泰新材料科技有限公司 Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate
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