CN112574551A - Modified nano calcium carbonate-polyurethane-polyamide foam and preparation method thereof - Google Patents
Modified nano calcium carbonate-polyurethane-polyamide foam and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified nano calcium carbonate-polyurethane-polyamide foam composite material which comprises the following components in percentage by weight: 45-55% of isocyanate, 5-15% of polyether, 4-8% of fatty acid modified nano calcium carbonate, 4-9% of methyl hexahydrophthalic anhydride, 4-6% of azodiisobutyronitrile, 7-12% of 2,3, 6-tris (dimethylaminomethyl) phenol, 12-20% of polyurethane fiber, 2-5% of n-pentane and 0.0001-1% of silicon foam stabilizer. The rigid foam composite material provided by the invention introduces polyurea and amide groups on the basis of rigid polyurethane foam synthesis, and further improves the system by utilizing the characteristics of nano calcium carbonate, so that the product has excellent mechanical properties and thermal stability.
Description
The technical field is as follows:
the invention relates to the technical field of polyurethane rigid foam, in particular to a modified nano calcium carbonate-polyurethane-polyamide rigid foam composite material and a preparation method thereof.
Background art:
the polyurethane rigid foam is a high-molecular thermosetting polymer, has good chemical stability, acid resistance, alkali resistance, heat resistance, freezing resistance, low-temperature flexibility and low water absorption rate, can well block the permeation of water and water vapor, keeps a good and stable heat insulation condition, and is a heat insulation plate material with excellent performance and optimal cost performance which is commonly adopted in the current market.
However, with the improvement of the requirements on the materials in the application, the existing hard polyurethane foam thermal insulation material has poor mechanical properties such as compression, tension and the like and poor heat resistance, has high production cost, and cannot meet the requirements of people in daily life, thereby influencing the application range of the hard polyurethane foam thermal insulation material.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a modified nano calcium carbonate-polyurethane-polyamide foam composite material and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows: a modified nano calcium carbonate-polyurethane-polyamide foam comprises the following components in percentage by weight:
45-55% of isocyanate, 5-15% of polyether, 4-8% of fatty acid modified nano calcium carbonate, 4-9% of methyl hexahydrophthalic anhydride, 4-6% of azodiisobutyronitrile, 7-12% of 2,3, 6-tris (dimethylaminomethyl) phenol, 12-20% of polyurethane fiber, 2-5% of n-pentane and 0.0001-1% of silicon foam stabilizer.
Preferably, the isocyanate is one or a combination of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, polymethylene polyphenylene polyisocyanate and alicyclic polyisocyanate.
Preferably, the particle size of the azodiisobutyronitrile is 300-500 meshes.
Preferably, the preparation method of the fatty acid modified nano calcium carbonate comprises the following steps:
uniformly mixing fatty acid and ethyl acetate according to the weight percentage of 1:1 to obtain a modifier solution; and respectively adding 88-98% of nano calcium carbonate and 2-12% of the modifier solution into a high-speed mixer, uniformly mixing at the rotating speed of 60rpm, reducing the rotating speed to 25rpm when the temperature reaches 105 ℃, and keeping for 0.5h to obtain the modified nano calcium carbonate.
Preferably, the fatty acid is one or more of caprylic acid, pelargonic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, elaidic acid, erucic acid, brassidic acid, sorbic acid.
Preferably, the fatty acid is lauric acid, oleic acid or stearic acid.
The invention also provides a preparation method of the modified nano calcium carbonate-polyurethane-polyamide foam, which comprises the following steps:
(1) quantitatively mixing polyether, foam stabilizer, n-pentane, azodiisobutyronitrile and methylhexahydrophenyl
The anhydride and the 2,3, 6-tris (dimethylaminomethyl) phenol are mixed evenly and mixed for 20-30min at 30rpm,
preparing a composition A;
(2) quantitatively modifying nano calcium carbonate, polyurethane fiber and isocyanate in
Stirring uniformly at 25-30 ℃, and homogenizing by using an emulsifying pump to obtain a mixed solution B;
(3) composition A and mixture B were mixed and stirred at 100rpm for 30 seconds and then poured in
Foaming and molding the mixture in a mold, standing for 1h to fully react and cure the foam to obtain an intermediate;
(4) demolding the intermediate, transferring into hot water of 65-70 deg.C, and maintaining the temperature for 2 hr;
(5) and after the constant temperature is finished, taking out the product, cooling for more than 10 hours, and machining into the required sample.
The invention has the beneficial effects that:
(1) the modified nano calcium carbonate-polyurethane-polyamide foam composite material provided by the invention introduces polyurea and amide groups on the basis of rigid polyurethane foam synthesis, and further improves the system by utilizing the characteristics of the modified nano calcium carbonate, so that the product has excellent mechanical properties and thermal stability.
(2) Due to the introduction of polyamide groups and nano calcium carbonate, the modified nano calcium carbonate with perfect and smooth crystal structure is easily distributed in the matrix after modification treatment, particles are not easy to separate from the matrix when being acted by external force, and a plurality of micro deformation regions are generated inside the matrix due to the interaction of stress fields, so that a large amount of energy is absorbed, and the compression performance of the invention is obviously improved.
(3) Because of the reinforcing effect of the nano particles, the nano calcium carbonate is cubic crystal, the surface layer is smooth, the thermal motion of surface atoms is more violent than that of internal atoms, and the number of the surface atoms accounts for a larger proportion, so the activity of the particles is high, the surface is modified twice, the particles can be well combined with polyurethane groups with strong polarity, the particles can be effectively dispersed in a collective body, the dispersion strengthening effect is realized, and the tensile strength of the invention is improved.
(4) In the scheme of the invention, the urethane fiber chain segment is introduced, so that the viscosity of the system is improved, the pre-toughness of the system is improved, the toughening effect of the inorganic nano calcium carbonate is increased, the foam body breakage is reduced in the impact damage process, and the impact strength is improved.
The specific implementation mode is as follows:
the following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly define the scope of the invention.
Example 1
A modified nano calcium carbonate-polyurethane-polyamide foam is prepared from the following components in percentage by weight:
45% of 2, 4-toluene diisocyanate, 5.5% of polyether, 8% of fatty acid modified nano calcium carbonate, 9% of methyl hexahydrophthalic anhydride, 4.5% of azobisisobutyronitrile (with the particle size of about 400 meshes), 12% of 2,3, 6-tris (dimethylaminomethyl) phenol, 12% of polyurethane fiber, 3.2% of n-pentane and 0.8% of silicon foam stabilizer.
In addition, because common nano calcium carbonate is mostly in a secondary agglomeration state, and the specifications of domestic calcium carbonate products are different, the quality is difficult to stabilize and uniform, the common nano calcium carbonate needs to be coated by a secondary dry method during application, firstly, the polar component of the surface energy of particles is further improved by using a modifier, secondly, redundant moisture is removed at high temperature, the residual moisture of the nano calcium in the material mixing process is prevented from reacting with isocyanate, thirdly, the nano calcium is dispersed again, and the uniformity of the surface coating of the nano calcium carbonate is further improved. The BET of the fatty acid modified nano calcium carbonate used in the invention is between 10 and 20m2The preparation method comprises the following steps:
uniformly mixing fatty acid and ethyl acetate according to the weight percentage of 1:1 to obtain a modifier solution; and respectively adding 90 wt% of nano calcium carbonate and 10 wt% of the modifier solution into a high-speed mixer, uniformly mixing at the rotating speed of 60rpm, reducing the rotating speed to 25rpm when the temperature reaches 105 ℃, and keeping for 0.5h to obtain the fatty acid modified nano calcium carbonate. The fatty acid is oleic acid.
In the invention, isocyanate in the system mainly has three types of reactions, namely, the reaction of isocyanate and hydroxyl, the self-polymerization reaction of isocyanate, the regulation of the reaction rate of the two types of reactions is regulated by a catalyst, the reaction of isocyanate and carboxyl and acid anhydride, and the reaction rate is regulated by temperature. When the hydroxyl group is derived from a water molecule, 1 water molecule reacts with 2 NCO groups to obtain a substituted urea, and water can be regarded as a chain extender or a curing agent. The temperature of the system can reach 130 ℃, and biuret crosslinking is formed in a small amount.
In addition, the foaming process in the system is as follows:
if the viscosity of the system is high, on one hand, the escape rate of gas is reduced, the dimensional stability is good, on the other hand, the foaming is difficult, the rigidity of amide and urea bonds is high, the cracking is easy to occur due to rapid expansion, and the low-density foam is difficult to obtain, and the problem can be solved by adopting a double foaming method.
The polyurethane foaming is promoted by gas generated by a reaction system, the traditional method has physical foaming agents such as n-pentane and the like, and the gas is formed by utilizing the gasification of the heat of the system reaction. Secondly, the isocyanate water foams to generate carbon dioxide gas, but the urea bond has large polarity and the chain segment has large rigidity, so that the matrix has high hardness, the pore wall is rough, and thick cells are formed. The problem can be solved by adding the chemical foaming agent, the AIBN with low decomposition temperature is added into the system, namely, the AIBN is decomposed by using waste heat while water foaming, gas is slowly released, and the gas, the n-pentane and carbon dioxide generated by water foaming jointly push the foaming process, so that foam formation is facilitated, the aperture ratio is low, the foam is not shrunk after the foaming reaction is completed, and the size stability is good. The density and mechanical properties can be controlled by the functionality of the isocyanate mixture and the amount of the two blowing agents, meeting the various requirements of production.
According to the scheme, a large amount of fatty acid modified nano calcium carbonate can be contained, and the hard polyurethane foam prepared by foaming can further improve the high temperature resistance and the compression resistance of the hard polyurethane foam due to the internal distribution of the nano calcium carbonate, so that the influence on the heat insulation performance of the hard polyurethane foam is small. And the nano calcium carbonate is used as an inorganic filler, plays a role in heterogeneous nucleation in the foaming process, is beneficial to uniform cells and reduces the diameter of the cells.
In addition, the fatty acid modified nano calcium carbonate has larger surface tension and reinforcing effect, so that a network formed in the polyurethane foaming process is not easy to break, and the composite material has good compression permanent deformation resistance.
Polyurethane fibers are required to be added in the formula, are prepared by spinning polyurethane serving as a raw material and have good bonding property with a rigid polyurethane foam matrix; the fiber has excellent performances of high modulus, high softness and the like, can influence the viscosity of a system in the foaming process, reduces the occurrence of cell breakage and cell string, plays a toughening role in the secondary foaming process, resists the tearing damage of a matrix, increases the binding force of the fatty acid modified nano calcium carbonate and a rigid polyurethane matrix, and plays an important role in improving the toughness and the dimensional stability of the rigid polyurethane foam.
The preparation method of the modified nano calcium carbonate-polyurethane-polyamide foam composite material in the embodiment comprises the following steps:
(1) quantitatively mixing polyether, foam stabilizer, n-pentane, azodiisobutyronitrile and methylhexahydrophenyl
Mixing anhydride and 2,3, 6-tris (dimethylaminomethyl) phenol uniformly, mixing at 30rpm for 20min to obtain the final product
A composition A;
(2) quantitatively modifying nano calcium carbonate, polyurethane fiber and isocyanate in
Stirring uniformly at 25 ℃, and homogenizing by using an emulsifying pump to obtain a mixed solution B;
(3) composition A and mixture B were mixed and stirred at 100rpm for 30 seconds and then poured in
Foaming and molding the mixture in a mold, standing for 1h to fully react and cure the foam to obtain an intermediate;
(4) demolding the intermediate, transferring into hot water of 65 ℃, and keeping the temperature for 2 hours;
(5) and after the constant temperature is finished, taking out the product, cooling for more than 10 hours, and machining into the required sample.
Example 2
A modified nano calcium carbonate-polyurethane-polyamide foam is prepared from the following components in percentage by weight:
48% of 2, 6-toluene diisocyanate, 9.8% of polyether, 4% of fatty acid modified nano calcium carbonate, 6.7% of methyl hexahydrophthalic anhydride, 5% of azobisisobutyronitrile (with the particle size of 350 meshes), 9.4% of 2,3, 6-tris (dimethylaminomethyl) phenol, 14% of polyurethane fiber, 3% of n-pentane and 0.1% of silicon foam stabilizer.
The preparation method of the fatty acid modified nano calcium carbonate comprises the following steps:
uniformly mixing fatty acid and ethyl acetate according to the weight percentage of 1:1 to obtain a modifier solution; and respectively adding 93 percent by weight of nano calcium carbonate and 7 percent by weight of the modifier solution into a high-speed mixer, uniformly mixing at the rotating speed of 60rpm, reducing the rotating speed to 25rpm when the temperature reaches 105 ℃, and keeping for 0.5h to obtain the fatty acid modified nano calcium carbonate. The fatty acid is lauric acid.
In the preparation method of the modified nano calcium carbonate-polyurethane-polyamide foam composite material of the embodiment, the mixing time in the step (1) is 26min, the stirring temperature in the step (2) is 28 ℃, the hot water temperature in the step (4) is 65 ℃, and other conditions are the same as those in the embodiment 1.
Example 3
A modified nano calcium carbonate-polyurethane-polyamide foam is prepared from the following components in percentage by weight:
50.8% of polymethylene polyphenylene polyisocyanate, 7.6% of polyether, 6% of fatty acid modified nano calcium carbonate, 7% of methyl hexahydrophthalic anhydride, 4% of azobisisobutyronitrile (particle size of 500 meshes), 9.5% of 2,3, 6-tris (dimethylaminomethyl) phenol, 12.5% of polyurethane fiber, 2.5% of n-pentane and 0.1% of silicon foam stabilizer.
The preparation method of the fatty acid modified nano calcium carbonate comprises the following steps:
uniformly mixing fatty acid and ethyl acetate according to the weight percentage of 1:1 to obtain a modifier solution; and respectively adding 95 wt% of nano calcium carbonate and 5 wt% of the modifier solution into a high-speed mixer, uniformly mixing at the rotating speed of 60rpm, reducing the rotating speed to 25rpm when the temperature reaches 105 ℃, and keeping for 0.5h to obtain the fatty acid modified nano calcium carbonate. The fatty acid is stearic acid.
In the preparation method of the modified nano calcium carbonate-polyurethane-polyamide foam composite material of the embodiment, the mixing time in the step (1) is 30min, the stirring temperature in the step (2) is 30 ℃, the hot water temperature in the step (4) is 68 ℃, and other conditions are the same as those in the embodiment 1.
The properties of the modified nanocalcium carbonate-polyurethane-polyamide foam composites of the invention were evaluated by the following tests, the results of which are detailed in table 1 for examples 1-3. The performances of the modified nano calcium carbonate-polyurethane-polyamide foam composite material and the performances of the common polyurethane foam such as compression performance, tensile strength, impact strength and the like are respectively detected.
As can be seen from table 1, the mechanical properties of the examples of the present invention are superior to those of the conventional polyurethane products on the market, compared to the conventional polyurethane foam, and the heat resistance of the composite rigid foam of the present invention is significantly improved due to the presence of polyamide and urea groups in addition to urethane groups. Compared with common polyurethane foam, the polyurethane foam has the advantages that the heat resistance, the impact property, the compressive strength and the tensile strength are obviously improved, and the service life and the application range of a polyurethane product are prolonged.
TABLE 1
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (7)
1. The modified nano calcium carbonate-polyurethane-polyamide foam is characterized by comprising the following components in percentage by weight:
45-55% of isocyanate, 5-15% of polyether, 4-8% of fatty acid modified nano calcium carbonate, 4-9% of methyl hexahydrophthalic anhydride, 4-6% of azodiisobutyronitrile, 7-12% of 2,3, 6-tris (dimethylaminomethyl) phenol, 12-20% of polyurethane fiber, 2-5% of n-pentane and 0.0001-1% of silicon foam stabilizer.
2. The modified nano calcium carbonate-polyurethane-polyamide foam according to claim 1, wherein the isocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, polymethylene polyphenylene polyisocyanate, and alicyclic polyisocyanate.
3. The modified nano calcium carbonate-polyurethane-polyamide foam as claimed in claim 1, wherein the particle size of azobisisobutyronitrile is 300-500 mesh.
4. The modified nano calcium carbonate-polyurethane-polyamide foam as claimed in claim 1, wherein the fatty acid modified nano calcium carbonate is prepared by the following steps:
uniformly mixing fatty acid and ethyl acetate according to the weight percentage of 1:1 to obtain a modifier solution; and respectively adding 88-98% of nano calcium carbonate and 2-12% of the modifier solution into a high-speed mixer, uniformly mixing at the rotating speed of 60rpm, reducing the rotating speed to 25rpm when the temperature reaches 105 ℃, and keeping for 0.5h to obtain the modified nano calcium carbonate.
5. The modified nano calcium carbonate-polyurethane-polyamide foam of claim 4, wherein the fatty acid is one or more of caprylic acid, pelargonic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, elaidic acid, erucic acid, brassidic acid, sorbic acid.
6. The modified nanocalcium carbonate-polyurethane-polyamide foam of claim 5, wherein the fatty acid is lauric acid, oleic acid, or stearic acid.
7. A process for the preparation of the modified nanocalcium carbonate-polyurethane-polyamide foam according to any one of claims 1 to 6, characterized in that it comprises the following steps:
(1) uniformly mixing a certain amount of polyether, a foam stabilizer, n-pentane, azodiisobutyronitrile, methyl hexahydrophthalic anhydride and 2,3, 6-tris (dimethylaminomethyl) phenol, and mixing at 30rpm for 20-30min to prepare a composition A;
(2) uniformly stirring a certain amount of fatty acid modified nano calcium carbonate, polyurethane fiber and isocyanate at 25-30 ℃, and homogenizing by using an emulsification pump to obtain a mixed solution B;
(3) mixing the composition A and the mixed solution B, stirring at 100rpm for 30 seconds, pouring into a mold for foaming and molding, standing for 1h to enable foams to fully react and cure to obtain an intermediate;
(4) demolding the intermediate, transferring into hot water of 65-70 deg.C, and maintaining the temperature for 2 hr;
(5) and after the constant temperature is finished, taking out the product, cooling for more than 10 hours, and machining into the required sample.
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