CN109535368B - Low-temperature-resistant polyurethane microporous material and preparation method thereof - Google Patents

Low-temperature-resistant polyurethane microporous material and preparation method thereof Download PDF

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CN109535368B
CN109535368B CN201811446573.1A CN201811446573A CN109535368B CN 109535368 B CN109535368 B CN 109535368B CN 201811446573 A CN201811446573 A CN 201811446573A CN 109535368 B CN109535368 B CN 109535368B
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microporous material
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polyurethane microporous
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CN109535368A (en
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邵琛
谢海明
朱东升
孙海珠
潘秀梅
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Northeast Normal University
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Abstract

The invention provides a low temperature resistant polyurethane microporous material and a preparation method thereof, and relates to the technical field of polyurethane microporous materials. Under the condition of low temperature, the change rate of the elastic modulus of the polyurethane microporous material is small, the hardness at the low temperature does not change greatly compared with the hardness at the normal temperature, and the polyurethane microporous material has the characteristics of low temperature resistance and fatigue resistance and higher mechanical performance. During preparation, the temperature required by the reaction is low, and the method is suitable for industrial production.

Description

Low-temperature-resistant polyurethane microporous material and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane microporous materials, in particular to a low-temperature-resistant polyurethane microporous material and a preparation method thereof.
Background
Polyurethane is a general name of a class of high polymer materials containing a plurality of repeated carbamate groups in a molecular structure, is mainly prepared from isocyanate, polyol, small molecular alcohol or amine through polycondensation, and comprises a soft segment and a hard segment in the structure. The isocyanate and the small molecular alcohol or amine are called hard segment components and are aggregated through hydrogen bond interaction to form a hard segment; the polyols are generally referred to as soft segments and aggregate to form soft segments. Polyurethanes are classified according to their uses and can be classified into polyurethane foams, polyurethane elastomers, polyurethane microcellular elastomers, polyurethane adhesives, polyurethane coatings, and polyurethane synthetic leather.
The microcellular polyurethane elastomer is a material with the performance between that of a polyurethane elastomer and that of a polyurethane foam material, the density is between that of the foam and that of a solid material, the pore diameter of the cells is 0.1 to hundreds of microns, and the pore diameter distribution is relatively uniform. The foam is characterized by light weight, good impact resistance, good energy absorption and buffering performance, high strength and good wear resistance of the elastomer, so that the microcellular polyurethane elastomer exceeds other microcellular elastomers with the same density in the aspect of main physical and mechanical properties, and is widely applied to the aspects of damping materials, shoe making, sealing, solid tires and filtering energy. Particularly, in the aspect of shock absorption, the absorption rate of the shock energy reaches 75-90%, the shock energy absorption rate is better than that of butyl rubber, the butyl rubber has high strength and high wear resistance, can be used as an excellent shock absorption material, and is widely applied to the fields of automobiles, high-speed rails and the like.
Because of the characteristics of the molecular structure of the microporous polyurethane material, molecular chains can crystallize to a certain degree in an extremely low temperature environment, the specific surface of the microporous polyurethane material has the defects of rapid hardness rise and elasticity loss, and the microporous polyurethane material can reduce the damping performance when being used as a damping material for automobiles, rail traffic and the like.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a low-temperature-resistant polyurethane microporous material and a preparation method thereof, so that the polyurethane microporous material has excellent low-temperature resistance, the elastic modulus change rate of the polyurethane microporous material is extremely low under a low-temperature condition, and the polyurethane microporous material can still play a role in shock absorption.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0001885865150000021
the component B comprises the following components in parts by weight:
Figure BDA0001885865150000022
preferably, the polyisocyanate is one or a mixture of p-phenylene diisocyanate and diphenylmethane diisocyanate.
Preferably, the side reaction inhibitor is one of an inorganic acid, an organic acid or benzenesulfonyl chloride.
Preferably, the diamine chain extender is one or a mixture of methylene bis-o-chloroaniline and 2, 4-diamino-5-mercaptotoluene.
Preferably, the tertiary amine is triethylene diamine formate, and the organotin catalyst is one or a mixture of dioctyl tin mercaptide and dialkyl tin dimaleate.
The preparation method of the low temperature resistant polyurethane microporous material comprises the following steps:
1) preparation of component A: placing hydrogenated hydroxyl-terminated butadiene polyol and polytetrahydrofuran ether polyol into a reaction kettle, dehydrating for 120min under the condition of 110-140 ℃ in vacuum with the vacuum degree of 200-300Pa, then cooling to 60-70 ℃, and introducing N2Gas, adding polyisocyanate and side reaction inhibitor into the reaction kettle in N2Reacting for 120-150min under the atmosphere, cooling to 45-50 ℃, and discharging to obtain a component A;
2) preparation of the component B: fully mixing hydrogenated hydroxyl-terminated butadiene polyol, polytetrahydrofuran ether polyol, a diamine chain extender, a tertiary amine or organic tin catalyst, a polyether modified organic silicon foam stabilizer and water in a reaction kettle at the temperature of 40-60 ℃, discharging after 180-min;
3) foaming and forming: controlling the temperature within the range of 35-45 ℃, adding the component B into the component A, fully mixing the two components, injecting into a mold at 80-100 ℃, and demolding after 45-75min to obtain a primary finished product;
4) annealing the primary finished product obtained in the step 3) for 24 hours at the temperature of 90-100 ℃, and then standing for 5-7 days at room temperature to obtain a finished product.
Preferably, the vacuum dehydration temperature in the step 1) is 130 ℃, and the vacuum degree is 200 pa.
Preferably, the mold temperature in step 3) is 100 ℃ and the annealing temperature in step 4) is 100 ℃.
In the invention, hydrogenated hydroxyl-terminated butadiene and polytetrahydrofuran ether mixed polyol is used as the soft phase, and benzene diisocyanate or diphenylmethane diisocyanate or a mixture of the two, and methylene bis-o-chloroaniline or 2, 4-diamino-5-mercaptotoluene is used as the hard phase. The hydrogenated hydroxyl-terminated butadiene polyol contains nonpolar carbon-carbon single bonds with rich conformation and soft carbon-carbon double bonds, and the polytetrahydrofuran ether polyol has a more regular molecular chain structure, lower cohesive energy and better soft type because ether groups can rotate more easily, so the hydrogenated hydroxyl-terminated butadiene polyol and the polytetrahydrofuran ether polyol are used as mixed polyol to prepare polyurethane micropores, and have excellent low-temperature resistance.
The soft segment crystallization can reduce the low-temperature flexibility of the material, the mixed chain extender of methylene bis-o-chloroaniline and 2, 4-diamino-5-mercaptotoluene is adopted to reduce the crystallinity of the soft segment, the low-temperature resistance of the polyurethane microporous material is further improved, the diamine chain extender can form a urea bond, the polarity of the urea bond is strong, the solubility parameter between the hard segment of the urea bond and the soft segment of polyether is greatly different, the hard segment and the soft segment have greater thermodynamic incompatibility, the polyurethane has better micro-phase separation, and the prepared polyurethane microporous material has higher mechanical strength, elastic modulus and better low-temperature resistance.
The invention uses one or a mixture of more of triethylene diamine formate, dioctyl tin mercaptide and dialkyl tin dimaleate as a delay catalyst, has better compatibility with the mixed polyol, is more stable, has longer operation time and does not influence the later curing of products.
(III) advantageous effects
The invention provides a low-temperature-resistant polyurethane microporous material and a preparation method thereof, wherein the polyurethane microporous material has small elastic modulus change rate under the low-temperature condition, and the hardness at low temperature does not change greatly compared with the hardness at normal temperature, so that the polyurethane microporous material has the characteristics of low-temperature resistance and fatigue resistance and higher mechanical property.
When the polyurethane microporous material is prepared, the viscosity of the component A system is low, the mixing uniformity of the components can be improved when the component B is added, the pore diameter of the polyurethane micropores is reduced, the distribution is uniform, the low-temperature resistance of the material is enhanced, the reaction temperature is low, and the polyurethane microporous material is suitable for industrial production.
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 low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein: the component A comprises the following components in parts by weight: 35 parts of hydrogenated hydroxyl-terminated butadiene polyol, 10 parts of polytetrahydrofuran ether polyol, 95 parts of p-phenylene diisocyanate and 220ppm of inorganic acid; the component B comprises the following components in parts by weight: 30 parts of hydrogenated hydroxyl-terminated butadiene polyol, 10 parts of polytetrahydrofuran ether polyol, 20 parts of methylene bis-o-chloroaniline, 4 parts of triethylene diamine formate, 2 parts of polyether modified organic silicon foam stabilizer and 5 parts of water.
The preparation method of the low temperature resistant polyurethane microporous material comprises the following steps:
1) preparation of component A: the hydrogenated hydroxyl-terminated butadiene polyol andputting the polytetrahydrofuran ether polyol into a reaction kettle, dehydrating for 120min under the condition of 140 ℃ and the vacuum degree of 250pa, then cooling to 70 ℃, and introducing N2Adding p-phenylene diisocyanate and inorganic acid into a reaction kettle in N2Reacting for 150min under the atmosphere, cooling to 50 ℃, and discharging to obtain a component A;
2) preparation of the component B: fully mixing hydrogenated hydroxyl-terminated butadiene polyol, polytetrahydrofuran ether polyol, methylene bis-o-chloroaniline, triethylene diamine formate, a polyether modified organic silicon foam stabilizer and water in a reaction kettle at the temperature of 60 ℃, and discharging after 240min to obtain a component B;
3) foaming and forming: controlling the temperature at 45 ℃, adding the component B into the component A, fully mixing the two components, injecting into a 100 ℃ mold, and demolding after 75min to obtain a primary finished product;
4) annealing the primary finished product obtained in the step 3) for 24 hours at the temperature of 100 ℃, and then standing for 7 days at room temperature to obtain a finished product.
Example 2:
a low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein: the component A comprises the following components in parts by weight: 15 parts of hydrogenated hydroxyl-terminated butadiene polyol, 20 parts of polytetrahydrofuran ether polyol, 80 parts of diphenylmethane diisocyanate and 150ppm of organic acid; the component B comprises the following components in parts by weight: 25 parts of hydrogenated hydroxyl-terminated butadiene polyol, 15 parts of polytetrahydrofuran ether polyol, 16 parts of 2, 4-diamino-5-mercaptotoluene, 3.5 parts of dioctyl tin mercaptide, 1.5 parts of polyether modified organosilicon foam stabilizer and 4.5 parts of water.
The preparation method of the low temperature resistant polyurethane microporous material comprises the following steps:
1) preparation of component A: putting hydrogenated hydroxyl-terminated butadiene polyol and polytetrahydrofuran ether polyol into a reaction kettle, dehydrating for 120min in vacuum at the temperature of 130 ℃ and the vacuum degree of 200pa, then cooling to 65 ℃, and introducing N2Adding diphenylmethane diisocyanate and organic acid into a reaction kettle in N2Reacting for 140min under the atmosphere, cooling to 45 ℃, and discharging to obtain a component A;
2) preparation of the component B: fully mixing hydrogenated hydroxyl-terminated butadiene polyol, polytetrahydrofuran ether polyol, 2, 4-diamino-5-mercaptotoluene, dioctyl tin mercaptide, polyether modified organic silicon foam stabilizer and water in a reaction kettle at the temperature of 50 ℃, discharging after 220min to obtain a component B;
3) foaming and forming: controlling the temperature at 40 ℃, adding the component B into the component A, fully mixing the two components, injecting into a 90 ℃ mold, and demolding after 45min to obtain a primary finished product;
4) annealing the primary finished product obtained in the step 3) for 24 hours at the temperature of 90 ℃, and then standing for 5 days at room temperature to obtain a finished product.
Example 3:
a low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein: the component A comprises the following components in parts by weight: 30 parts of hydrogenated hydroxyl-terminated butadiene polyol, 5 parts of polytetrahydrofuran ether polyol, 83 parts of a mixture of benzene diisocyanate and diphenylmethane diisocyanate, and 40ppm of benzene sulfonyl chloride; the component B comprises the following components in parts by weight: 20 parts of hydrogenated hydroxyl-terminated butadiene polyol, 15 parts of polytetrahydrofuran ether polyol, 24 parts of 2, 4-diamino-5-mercaptotoluene, 2.2 parts of dialkyl tin dimaleate, 1 part of polyether modified organosilicon foam stabilizer and 3 parts of water.
The preparation method of the low temperature resistant polyurethane microporous material comprises the following steps:
1) preparation of component A: putting hydrogenated hydroxyl-terminated butadiene polyol and polytetrahydrofuran ether polyol into a reaction kettle, dehydrating for 120min under the condition of 110 ℃ in vacuum with the vacuum degree of 300pa, then cooling to 60 ℃, and introducing N2Adding the mixture of benzene diisocyanate and diphenylmethane diisocyanate and benzene sulfonyl chloride into a reaction kettle in N2Reacting for 120min under the atmosphere, cooling to 45 ℃, and discharging to obtain a component A;
2) preparation of the component B: fully mixing hydrogenated hydroxyl-terminated butadiene polyol, polytetrahydrofuran ether polyol, 2, 4-diamino-5-mercaptotoluene, dialkyl tin dimaleate, polyether modified organic silicon foam stabilizer and water in a reaction kettle at the temperature of 40 ℃, discharging after 180min to obtain a component B;
3) foaming and forming: controlling the temperature at 35 ℃, adding the component B into the component A, fully mixing the two components, injecting into a mold at 80 ℃, and demolding after 70min to obtain a primary finished product;
4) annealing the primary finished product obtained in the step 3) for 24 hours at the temperature of 95 ℃, and then standing for 6 days at room temperature to obtain a finished product.
Example 4:
a low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein: the component A comprises the following components in parts by weight: 20 parts of hydrogenated hydroxyl-terminated butadiene polyol, 15 parts of polytetrahydrofuran ether polyol, 92 parts of p-phenylene diisocyanate and 130ppm of inorganic acid; the component B comprises the following components in parts by weight: 22 parts of hydrogenated hydroxyl-terminated butadiene polyol, 20 parts of polytetrahydrofuran ether polyol, 15 parts of a mixture of methylene bis-o-chloroaniline and 2, 4-diamino-5-mercaptotoluene, 2.5 parts of a mixture of dioctyl tin mercaptide and dialkyl tin dimaleate, 0.5 part of polyether modified organosilicon foam stabilizer and 2 parts of water.
The preparation method of the low temperature resistant polyurethane microporous material comprises the following steps:
1) preparation of component A: putting hydrogenated hydroxyl-terminated butadiene polyol and polytetrahydrofuran ether polyol into a reaction kettle, dehydrating for 120min at 120 ℃ in vacuum with the vacuum degree of 300pa, cooling to 65 ℃, and introducing N2Gas, adding polyisocyanate and side reaction inhibitor into the reaction kettle in N2Reacting for 140min under the atmosphere, cooling to 50 ℃, and discharging to obtain a component A;
2) preparation of the component B: fully mixing hydrogenated hydroxyl-terminated butadiene polyol, polytetrahydrofuran ether polyol, methylene bis-o-chloroaniline, a mixture of dioctyl tin mercaptide and dialkyl tin dimaleate, a polyether modified organic silicon foam stabilizer and water in a reaction kettle at the temperature of 55 ℃, discharging after 200min to obtain a component B;
3) foaming and forming: controlling the temperature within 40 ℃, adding the component B into the component A, fully mixing the two components, injecting into a mold at 95 ℃, and demolding after 60min to obtain a primary finished product;
4) annealing the primary finished product obtained in the step 3) for 24 hours at the temperature of 100 ℃, and then standing for 5 days at room temperature to obtain a finished product.
Example 5:
a low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein: the component A comprises the following components in parts by weight: 32 parts of hydrogenated hydroxyl-terminated butadiene polyol, 18 parts of polytetrahydrofuran ether polyol, 90 parts of p-phenylene diisocyanate and 100ppm of inorganic acid; the component B comprises the following components in parts by weight: 26 parts of hydrogenated hydroxyl-terminated butadiene polyol, 13 parts of polytetrahydrofuran ether polyol, 25 parts of methylene bis-o-chloroaniline, 2 parts of triethylene diamine formate, 1 part of polyether modified organic silicon foam stabilizer and 3.5 parts of water. The preparation method of the low temperature resistant polyurethane microporous material is the same as that of the example 1.
Example 6:
a low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein: the component A comprises the following components in parts by weight: 25 parts of hydrogenated hydroxyl-terminated butadiene polyol, 12 parts of polytetrahydrofuran ether polyol, 85 parts of p-phenylene diisocyanate and 80ppm of inorganic acid; the component B comprises the following components in parts by weight: 24 parts of hydrogenated hydroxyl-terminated butadiene polyol, 12 parts of polytetrahydrofuran ether polyol, 18 parts of methylene bis-o-chloroaniline, 1.5 parts of triethylene diamine formate, 1.5 parts of polyether modified organic silicon foam stabilizer and 2.5 parts of water. The preparation method of the low temperature resistant polyurethane microporous material is the same as that of the example 1.
Example 7:
a low temperature resistant polyurethane microporous material is formed by the reaction of a component A and a component B, wherein: the component A comprises the following components in parts by weight: 18 parts of hydrogenated hydroxyl-terminated butadiene polyol, 19 parts of polytetrahydrofuran ether polyol, 88 parts of p-phenylene diisocyanate and 180ppm of inorganic acid; the component B comprises the following components in parts by weight: 28 parts of hydrogenated hydroxyl-terminated butadiene polyol, 8 parts of polytetrahydrofuran ether polyol, 22 parts of methylene bis-o-chloroaniline, 3 parts of triethylene diamine formate, 1 part of polyether modified organic silicon foam stabilizer and 1.5 parts of water. The preparation method of the low temperature resistant polyurethane microporous material is the same as that of the example 1.
The finished products obtained in examples 1 to 7 were subjected to performance tests, the test results being shown in table 1:
table 1:
Figure BDA0001885865150000081
Figure BDA0001885865150000091
in summary, the embodiment of the invention has the following beneficial effects: the low temperature resistant polyurethane microporous materials prepared in the examples 1 to 7 have the characteristics of low temperature resistance, fatigue resistance and the like, under the low temperature condition of 0 to-30 ℃, the elastic modulus change rate of the examples 1 to 7 is less than or equal to 10 percent, the tensile strength is more than or equal to 6.2MPa, the elongation at break is more than or equal to 550 percent, the fatigue resistance is more than or equal to 40 ten thousand times without damage, and the hardness is not changed much compared with the hardness at normal temperature, so the low temperature resistant polyurethane microporous materials are particularly suitable for the fields of automobiles, rail transportation and the like.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. A low temperature resistant polyurethane microporous material is characterized by being formed by reacting a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure FDA0001885865140000011
the component B comprises the following components in parts by weight:
Figure FDA0001885865140000012
2. the low temperature resistant polyurethane microporous material according to claim 1, wherein the polyisocyanate is one or a mixture of p-phenylene diisocyanate or diphenylmethane diisocyanate.
3. The low temperature resistant polyurethane microporous material according to claim 1, wherein the side reaction inhibitor is one of an inorganic acid, an organic acid or benzenesulfonyl chloride.
4. The low temperature resistant polyurethane microporous material according to claim 1, wherein the diamine chain extender is one or a mixture of methylene bis-o-chloroaniline or 2, 4-diamino-5-mercaptotoluene.
5. The low temperature resistant polyurethane microporous material according to claim 1, wherein the tertiary amine is triethylene diamine formate, and the organic tin catalyst is one of dioctyl tin mercaptide, dialkyl tin dimaleate or a mixture of the two.
6. The method for preparing a low temperature resistant polyurethane microporous material according to any one of claims 1 to 5, comprising the steps of:
1) preparation of component A: placing hydrogenated hydroxyl-terminated butadiene polyol and polytetrahydrofuran ether polyol into a reaction kettle, dehydrating for 120min under the condition of 110-140 ℃ in vacuum with the vacuum degree of 200-300Pa, then cooling to 60-70 ℃, and introducing N2Gas, adding polyisocyanate and side reaction inhibitor into the reaction kettle in N2Reacting for 120-150min under the atmosphere, cooling to 45-50 ℃, and discharging to obtain a component A;
2) preparation of the component B: fully mixing hydrogenated hydroxyl-terminated butadiene polyol, polytetrahydrofuran ether polyol, a diamine chain extender, a tertiary amine or organic tin catalyst, a polyether modified organic silicon foam stabilizer and water in a reaction kettle at the temperature of 40-60 ℃, discharging after 180-min;
3) foaming and forming: controlling the temperature within the range of 35-45 ℃, adding the component B into the component A, fully mixing the two components, injecting into a mold at 80-100 ℃, and demolding after 45-75min to obtain a primary finished product;
4) annealing the primary finished product obtained in the step 3) for 24 hours at the temperature of 90-100 ℃, and then standing for 5-7 days at room temperature to obtain a finished product.
7. The method for preparing a low temperature resistant polyurethane microporous material according to claim 5, wherein the vacuum dehydration temperature in step 1) is 130 ℃ and the vacuum degree is 200 pa.
8. The method of claim 5, wherein the mold temperature in step 3) is 100 ℃ and the annealing temperature in step 4) is 100 ℃.
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