CN113072738B - Polyurethane-silicon hybrid aerogel and preparation method thereof - Google Patents
Polyurethane-silicon hybrid aerogel and preparation method thereof Download PDFInfo
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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
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Abstract
The invention provides a polyurethane-silicon hybrid aerogel and a preparation method thereof, wherein polyether glycol and diisocyanate are subjected to polymerization reaction under the catalysis of a polymerization catalyst to obtain an isocyanate-terminated polyurethane oligomer, monoamino siloxane is added to obtain a siloxane-terminated polyurethane oligomer, an aqueous solution of a gel catalyst is added, and wet gel after gelation and aging is subjected to solvent replacement and supercritical drying to obtain the polyurethane-silicon hybrid aerogel. According to the invention, through a special preparation process, the obtained polyurethane-silicon hybrid aerogel has high resilience on the basis of ensuring high-temperature performance, and the technical problem that the high-resilience aerogel cannot be prepared in the prior art is solved.
Description
Technical Field
The invention relates to a polyurethane-silicon hybrid aerogel and a preparation method thereof, belonging to the technical field of aerogel preparation.
Background
The aerogel is a nano porous material formed by mutually coalescing colloidal particles or high polymer molecules, has the characteristics of low density, high specific surface area, low thermal conductivity and the like, and has very wide application prospect in the fields of aerospace vehicle thermal control systems, civil heat preservation and the like.
At present, most aerogel of report does not have the resilience, receives under the exogenic action, and in case the aerogel takes place deformation, the pore structure can take place to destroy, and the pore structure collapses even, leads to the heat-proof quality decline of aerogel, seriously influences the heat-proof quality stability of aerogel under long-term atress environment.
At present, the public reports on polyurethane aerogel can realize effective regulation and control of rigidity and flexibility by adjusting the ratio of the soft segment (polyol polymer) to the hard segment (polyisocyanate) structure, but no report on the research on the rebound resilience performance is found. For example, CN108285520A discloses an interpenetrating aerogel of polyurethane-polyurea structure, which is prepared by copolymerizing a polyisocyanate compound, a hydroxyl compound, and an amino compound, and performing supercritical drying. Because the molecular weight of the hydroxyl compound is not more than 400, the soft segment proportion of the molecular structure is low, and the hard segment proportion is high, the polyurethane aerogel prepared by the hydroxyl compound is rigid; the polyurea aerogel is prepared from polyisocyanate and micromolecular polyamino monomer, and the whole molecular structure is rigid, so that the prepared composite aerogel is also rigid.
Abhishek Bang et al synthesized a flexible, foldable PU aerogel, but did not investigate the resilience of the aerogel. (Bang A, buback C, sotiriou-Levens C, levens N.Flexibele aerogels from highly branched polyurethanes: combining the role of molecular criteria with poly (urethane acrylates) versals poly (urethane nonnodes) [ J ]. Chem. Mater.,2014,26 (24): 6979-6993.)
However, the use temperature of polyurethane is generally not more than 200 ℃, so that the use temperature of polyurethane aerogel is limited, and inorganic modification of polyurethane is a common method for improving the temperature resistance of polyurethane. For example, CN109422864A discloses a polyurethane-silicon based composite aerogel, which is prepared by preparing silica rigid beads with amino groups on the surface, and reacting rigid isocyanate and isocyanate oligomer containing a small amount of soft segments with the amino groups on the silica rigid beads to form a three-dimensional network structure. Because the whole molecular structure takes silicon dioxide as a rigid skeleton structure, the polyurethane-silicon-based composite aerogel is rigid and has no resilience.
The preparation of the polyurethane aerogel has the technical problem that the high temperature resistance and the high resilience conflict with each other, and how to organically combine the resilience with the high temperature resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-resilience and high-temperature-resistance polyurethane-silicon hybrid aerogel and a preparation method thereof.
The technical scheme of the invention is as follows: a preparation method of polyurethane-silicon hybrid aerogel is realized by the following steps:
in a first step, a solution of a siloxane-terminated polyurethane oligomer is prepared,
a1.1, uniformly mixing diisocyanate, polyether diol, a polymerization catalyst and a solvent to perform a polymerization end-capping reaction to obtain an isocyanate end-capped polyurethane oligomer solution;
a1.2, adding monoamino siloxane into the isocyanate-terminated polyurethane oligomer solution obtained in the step A1.1, and carrying out end-capping reaction on the isocyanate-terminated polyurethane oligomer to obtain siloxane-terminated polyurethane-silicon hybrid oligomer solution;
secondly, adding a water solution of a gel catalyst into the siloxane-terminated polyurethane-silicon hybrid oligomer solution prepared in the first step, uniformly mixing, standing, and aging after a reaction system gels to obtain polyurethane-silicon hybrid wet gel;
and thirdly, carrying out solvent replacement and supercritical drying on the polyurethane-silicon hybrid wet gel prepared in the second step to obtain the polyurethane-silicon hybrid aerogel.
A polyurethane-silicon hybrid aerogel prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, through a special preparation process, the obtained polyurethane-silicon hybrid aerogel has high resilience on the basis of ensuring high-temperature performance, and the technical problem that the high-resilience aerogel cannot be prepared in the prior art is solved;
(2) Firstly synthesizing an isocyanate terminated polyurethane oligomer with rebound resilience, grafting siloxane groups at the tail end, and then performing hydrolytic condensation on siloxane to form cross-linking points by a sol-gel process to form a cross-linking network mainly comprising a high-rebound flexible chain segment, so that the molecular structure of the high-rebound polyurethane is organically combined with the cross-linking structure of the high-temperature resistant silicon dioxide, and the high-rebound polyurethane-silicon hybrid aerogel is prepared;
(3) The aerogel heat insulation material has high resilience, can ensure the heat insulation performance stability in a long-term stress environment, and can expand the use scene of the aerogel;
(4) The invention can realize the effective regulation of the resilience of the polyurethane-silicon hybrid aerogel by regulating the molecular weight of the polyether diol;
(5) The method has the characteristics of wide applicability, cheap and easily-obtained raw materials, simple reaction process, low overall cost and the like, and the obtained material has a micro-nano-scale multi-level microstructure.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a SEM photograph of example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples and accompanying drawings.
The invention provides a preparation method of polyurethane-silicon hybrid aerogel, which is realized by the following steps as shown in figure 1:
in a first step, a solution of a siloxane-terminated urethane oligomer is prepared.
A1.1, uniformly mixing diisocyanate, polyether diol, a polymerization catalyst and a solvent to perform a polymerization end-capping reaction to obtain an isocyanate end-capped polyurethane oligomer solution.
In the step, a solvent can be added into the reaction system according to the requirement, the type of the solvent is a conventional aprotic strong polar solvent, and the solvent can be one or more of DMF, NMP, DMAc and the like which are conventionally used.
In the step, the polymerization temperature is not higher than 130 ℃, and not too high, so that isocyanate can generate side reaction to generate isocyanate tripolymer, and gel of a polymerization system can be generated; the polymerization temperature is not higher than 50 ℃, the polymerization temperature is not too low, and if the polymerization temperature is too low, the effect of promoting the polymerization reaction is not obvious; the polymerization temperature is preferably from 60 to 120 ℃.
The polymerization time in the step is not less than 5h, and if the polymerization time is too short, OH in a polymerization reaction system can not be completely reacted with isocyanate groups; the polymerization time is generally not too long, which reduces the preparation efficiency; the polymerization time is preferably 6 to 8 hours.
In this step, the molar ratio of polyether diol to diisocyanate is preferably 1: and 2, free polyether diol and diisocyanate are not contained in the obtained isocyanate-terminated polyurethane oligomer solution, so that the molecular structure design is facilitated, and the effective adjustment of the resilience of the polyurethane-silicon hybrid aerogel is easier to realize.
In this step, the kind of the polyether diol is not particularly limited, and may be one or more of common polyoxypropylene diol and polytetrahydrofuran diol. The polyether glycol plays a role in improving the flexibility and toughness of a molecular structure, the molecular weight of the polyether glycol cannot be too low and is generally not lower than 400, otherwise, the prepared polyurethane-silicon hybrid aerogel is rigid and has no resilience; the molecular weight of the polyether diol should not be too high, typically not higher than 2500, otherwise the polyurethane-silicone hybrid aerogel would be too flexible and not resilient. The molecular weight of the polyether glycol is preferably 600-2000, and in the range, the polyurethane-silicon hybrid aerogel is ensured to have high resilience and can keep a micro-nano porous structure. Other conditions are unchanged, and within the molecular weight range of the polyether glycol preferably required by the invention, the smaller the molecular weight of the polyether glycol, the larger the specific surface area of the obtained polyurethane-silicon hybrid aerogel is, and the better the rebound resilience is.
The diisocyanate in this step is not particularly limited, and may be one or more of aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, and the like, which are generally used in the art.
The kind of polyether diol and diisocyanate is selected by those skilled in the art according to the actual need.
In this step, the polymerization catalyst plays a role in promoting the polyether diol and the diisocyanate to perform a polymerization reaction, and the type of the polymerization catalyst is not particularly limited as long as the polymerization catalyst can play the above role, and the polymerization catalyst may be common triethylamine, dibutyltin dilaurate, stannous octoate, or the like. The dosage of the polymerization catalyst is not too much, otherwise, the isocyanate can generate side reaction to generate isocyanate trimer, so that the gel of a polymerization system is generally not higher than 2% of the mass sum of the polyether diol and the diisocyanate; if the content of the polymerization catalyst is too small, the polymerization reaction of the polyether diol and the diisocyanate is incomplete, and generally not less than 0.1% of the sum of the masses of the polyether diol and the diisocyanate. The skilled person will select the appropriate type and amount according to the actual situation.
And A1.2, adding monoamino siloxane into the isocyanate-terminated polyurethane oligomer solution obtained in the step A1.1, and carrying out end-capping reaction on the isocyanate-terminated polyurethane oligomer to obtain a siloxane-terminated polyurethane-silicon hybrid oligomer solution.
In the step, diisocyanate and monoamino siloxane are preferably in an equimolar ratio, so that the obtained siloxane-terminated polyurethane-silicon hybrid oligomer solution has no free monoamino siloxane or unblocked isocyanate-terminated polyurethane oligomer, and small molecular free matters cannot exist in the subsequent gel reaction to influence the resilience of the polyurethane-silicon hybrid aerogel.
In the step, the reaction temperature is not too high, generally not higher than 130 ℃, and if the reaction temperature is too high, the isocyanate is subjected to side reaction to generate isocyanate trimer, so that a reaction system is gelled; the reaction temperature cannot be too low, and if the reaction temperature is too low, the effect of promoting the reaction is not obvious; the reaction temperature is preferably from room temperature to 120 ℃.
In the step, the reaction time cannot be too short, and if the reaction time is too short, the amino group and the isocyanate group in the reaction system cannot be completely reacted; the reaction time is not too long, and the preparation efficiency is reduced; the reaction time is preferably 2 to 6 hours.
The step has no special requirement on the monoamino siloxane, and can be one or more of 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
And secondly, adding a water solution of a gel catalyst into the siloxane-terminated polyurethane-silicon hybrid oligomer solution prepared in the first step, uniformly mixing, standing, and aging after a reaction system gels to obtain the polyurethane-silicon hybrid wet gel.
In the step, the gel catalyst plays a role in promoting the siloxane and water to hydrolyze and condense to form a cross-linked network, and the type of the gel catalyst is not particularly limited as long as the gel catalyst can play the above role, and the gel catalyst can be common ammonia water, triethylamine, ethylenediamine, dibutyltin dilaurate, stannous octoate, ammonium fluoride and the like. The concentration of the gel catalyst cannot be too high, otherwise, the reaction system is too fast to gel, the operation is not facilitated, and the concentration is generally not higher than 1mol/L; if the concentration of the gel catalyst is too low, the reaction system will gel too slowly, and the wet gel strength is too poor, which is not favorable for the subsequent aerogel preparation step, and is generally not less than 0.1mol/L. The skilled person will select the appropriate species and concentration depending on the actual situation.
The water in the aqueous gel catalyst solution used in the siloxane hydrolysis reaction in this step is preferably a mono-aminosiloxane in a molar ratio to water in the aqueous solution of not more than 2: and 3, ensuring that the siloxane functional group is fully hydrolyzed.
The aging in the step is a necessary step for promoting the crosslinking network of the wet gel to be more perfect and improving the strength of the wet gel. The aging temperature is generally not more than 100 ℃, not less than 0 ℃, preferably between room temperature and 100 ℃, and the aging time is not less than 24 hours, and the aging temperature and the aging time are determined by a person skilled in the art according to actual needs.
And thirdly, carrying out solvent replacement and supercritical drying on the polyurethane-silicon hybrid wet gel prepared in the second step to obtain the polyurethane-silicon hybrid aerogel.
The solvent replacement in this step is a technique known in the art, and a person skilled in the art can select a solvent and a process according to specific situations.
The siloxane plays a role of a cross-linking point of a reaction system, and forms a silicon dioxide cross-linking network under the catalysis of a gel catalyst, so that a polyurethane-silicon hybrid gel network structure is realized (a molecular main chain is a linear polyurethane molecular chain segment, and the cross-linking point is a silicon dioxide structure); in the molecular structure, polyether diol is a soft segment and provides flexibility and toughness for a gel structure, isocyanate and a silicon dioxide structure are hard segments and provides rigidity for the gel structure, and the micro-nano porous structure is formed by regulating and controlling the proportion of the soft segment to the hard segment and inducing the micro-phase separation in the polyurethane-silicon hybrid aerogel, so that the high resilience performance of the polyurethane-silicon hybrid aerogel is realized.
According to the invention, isocyanate terminated polyurethane oligomer with rebound resilience is synthesized, siloxane groups are grafted at the tail end, and then siloxane is hydrolyzed and condensed to form cross-linking points through a sol-gel process, so that a cross-linking network mainly comprising a high-rebound flexible chain segment is formed, and the organic combination of a high-rebound polyurethane molecular structure and a high-temperature resistant silicon dioxide cross-linking structure is realized, thereby preparing the high-rebound polyurethane-silicon hybrid aerogel.
The invention further provides polyurethane-silicon hybrid aerogel, which is prepared by carrying out polymerization reaction on polyether glycol and diisocyanate under the catalysis of a polymerization catalyst to obtain isocyanate-terminated polyurethane oligomer, adding monoamino siloxane to obtain siloxane-terminated polyurethane oligomer, adding an aqueous solution of a gel catalyst, carrying out gel and aging on wet gel, and then carrying out solvent replacement and supercritical drying.
Further, the molar ratio of the polyether diol to the diisocyanate to the monoamino siloxane is 1:2:2, the water molar ratio of the monoamino siloxane to the gel catalyst in the water solution is not more than 2:3.
example 1
1. 60g of polytetrahydrofuran (molecular weight 600, 0.1mol), 50.05g of diphenylmethane diisocyanate (MDI, 0.2 mol) and 1.10g of dibutyltin dilaurate were dissolved in 990.45g of DMF, and reacted at 80 ℃ for 6 hours under mechanical stirring to obtain an isocyanate-terminated polyurethane oligomer solution; 44.28g (0.2 mol) of 3-aminopropyltriethoxysilane were added and reacted at 80 ℃ for 4h with mechanical stirring to give a solution of siloxane-terminated polyurethane-silicon hybrid oligomer.
2. And adding 10.8g of ammonia water solution (0.6 mol/L) into the siloxane-terminated polyurethane-silicon hybrid oligomer solution prepared in the first step, uniformly mixing, pouring into a mold, standing, and aging for 24 hours at 80 ℃ after a reaction system is gelled to obtain the polyurethane-silicon hybrid wet gel.
3. Performing solvent replacement on the condensed type organic silicon resin wet gel obtained in the step 2, repeatedly soaking the gel in ethanol for 3 times, and performing supercritical CO 2 Drying at 50 deg.C under 15MPa for 8 hr to obtain high resilience polyurethane-silicon hybrid aerogel.
The density of the high-resilience polyurethane-silicon hybrid aerogel obtained in the example is 0.18g/cm 2 The SEM photograph is shown in figure 2.
As can be seen from the scanning electron micrograph of fig. 1, this example successfully prepared a high resilience polyurethane-silica hybrid aerogel of the expected structure, and the aerogel microstructure was a micro-nano porous structure; air atmosphere, 5% weight loss temperature of 315 ℃.
Example 2
The conditions and procedure for the preparation of the high resilience polyurethane-silica hybrid aerogel were the same as in example 1 except that polytetrahydrofuran having a molecular weight of 1000, a mass of 100g, dibutyltin dilaurate having a mass of 1.50g, and DMF having a mass of 1350.45g was added, and the aerogel density was 0.19g/cm 2 。
Example 3
The conditions and procedure for the preparation of the high resilience polyurethane-silica hybrid aerogel were the same as in example 1 except that polytetrahydrofuran having a molecular weight of 2000, a mass of 200g, dibutyltin dilaurate having a mass of 2.50g and DMF having a mass of 2250.45g was added, and the aerogel density was 0.21g/cm 2 。
Example 4
The conditions and procedure for preparing the high resilience polyurethane-silicone hybrid aerogel were the same as in example 2 except that the polyether glycol added was polyoxypropylene glycol, and the aerogel density was 0.20g/cm 2 。
Example 5
Preparation conditions for the high-resilience polyurethane-silicone hybrid aerogel and were such that, except for the fact that the diisocyanate added was hydrogenated phenylmethane diisocyanate and had a mass of 52.47g, dibutyltin dilaurate and DMF of 2268.45g, the mass of the polyurethane-silicone hybrid aerogel was highThe procedure was as in example 2, the aerogel density being 0.22g/cm 2 。
Specific surface areas of examples 1 to 5 (samples were subjected to vacuum degassing at 100 ℃ C. For 10 hours before the test), TGA (temperature rising rate: 10 ℃ C./min, air flow rate: 100mL/min, temperature range: 100 to 800 ℃ C.). The test results are shown in Table 1.
TABLE 1
The difference in properties of examples 1 to 3 is a result of the difference in the ratio of soft to hard segments in the molecular structure of the high resilience polyurethane-silica hybrid aerogel, and as the molecular weight of the polyether diol decreases, the ratio of soft segments decreases, the density of the sample decreases, and both the specific surface area and the resilience tend to increase.
In examples 2, 4 and 5, the difference in properties is caused by the difference in molecular structure.
The temperature of 5 percent weight loss of the polyurethane materials in the embodiments 1 to 5 is higher than 290 ℃, is far higher than the decomposition temperature (generally not higher than 200 ℃) of the traditional polyurethane materials, and has better temperature resistance and wider temperature range application range.
The invention has not been described in detail and is not limited thereto.
Claims (10)
1. The preparation method of the polyurethane-silicon hybrid aerogel is characterized by comprising the following steps of:
in a first step, a solution of a siloxane-terminated polyurethane oligomer is prepared,
a1.1, uniformly mixing diisocyanate, polyether diol, a polymerization catalyst and a solvent for a polymerization end-capping reaction to obtain an isocyanate end-capped polyurethane oligomer solution, wherein the molecular weight of the polyether diol is not less than 400 and not more than 2500;
a1.2, adding monoamino siloxane into the isocyanate-terminated polyurethane oligomer solution obtained in the step A1.1, and carrying out end-capping reaction on the isocyanate-terminated polyurethane oligomer to obtain siloxane-terminated polyurethane-silicon hybrid oligomer solution;
secondly, adding a water solution of a gel catalyst into the siloxane-terminated polyurethane-silicon hybrid oligomer solution prepared in the first step, uniformly mixing, standing, and aging after a reaction system gels to obtain polyurethane-silicon hybrid wet gel;
and thirdly, carrying out solvent replacement and supercritical drying on the polyurethane-silicon hybrid wet gel prepared in the second step to obtain the polyurethane-silicon hybrid aerogel.
2. The method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: in the step A1.1, the molar ratio of the polyether diol to the diisocyanate is 1:2.
3. the method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: the molecular weight of the polyether diol in the step A1.1 is 600-2000.
4. The method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: the polymerization end capping reaction temperature in the step A1.1 is 60-120 ℃, and the reaction time is 6-8 h.
5. The method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: in step A1.2, the diisocyanate and the monoamino siloxane are in an equimolar ratio.
6. The method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: in the step A1.2, the reaction temperature is between room temperature and 120 ℃, and the reaction time is between 2 and 6 hours.
7. The method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: the molar ratio of the monoamino siloxane to the water in the aqueous gel catalyst solution in the second step is not more than 2:3.
8. the method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: the concentration of the gel catalyst aqueous solution in the second step is 0.1-1 mol/L.
9. The method for preparing a polyurethane-silica hybrid aerogel according to claim 1, wherein: and in the third step, the aging temperature is between room temperature and 100 ℃, and the aging time is not less than 24 hours.
10. A polyurethane-silica hybrid aerogel prepared by the method of any of claims 1-9.
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