CN110105525B - NDI-based polyurethane microporous elastomer resistant to damp-heat aging and preparation method thereof - Google Patents
NDI-based polyurethane microporous elastomer resistant to damp-heat aging and preparation method thereof Download PDFInfo
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Abstract
The invention provides a damp-heat aging resistant NDI (neutral density index) -based polyurethane microporous elastomer and a preparation method thereof. The NDI-based polyurethane microporous elastomer is prepared from a component A and a component B according to the mass ratio of 100: (2.3-9.6), wherein the component A comprises the following raw materials: polycarbonate modified polycaprolactone polyol, polyester polyol, bio-based polyol, a polymerization inhibitor and diisocyanate; the component B comprises the following raw materials: chain extender, cross linker, catalyst, foam stabilizer and foaming agent. The NDI-based polyurethane microporous elastomer has excellent wet-heat-aging resistance, good hydrolysis resistance, low-temperature flexibility and physical and mechanical properties, and can completely meet the use requirements under severe weather conditions such as high temperature and high humidity. The preparation method has the advantages of short process flow, simple operation, low process cost and high production efficiency, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to a damp-heat aging resistant NDI (neutral density index) -based polyurethane microporous elastomer and a preparation method thereof.
Background
The NDI-based polyurethane material has a microstructure, a molecular chain segment contains naphthalene ring structural units, the rigidity of the molecular chain is stronger than that of a benzene ring, and macroscopically shows that the NDI-based polyurethane microporous elastomer has higher stiffness and very good mechanical properties. The NDI-based polyurethane material is generally prepared by polymerizing polyester polyol and NDI and then extending a chain, but because a polyester system contains a large amount of ester groups, when the polyester material is exposed in the presence of water molecules, particularly in a high-temperature high-humidity environment, the aging rate of the material is accelerated, the service life of a product is seriously influenced, and if the polyester material is replaced by the polyether polyol or the polyether and the polyester are compounded, although the wet-heat aging resistance is relieved, the mechanical strength is too low, and the use of the product is limited.
At present, a prepolymer is polymerized mostly by adopting a mode of polyester polyol containing side groups or polyadipate-polyether copolyol or compounding polyadipate and polyether to improve the water-aging resistance of the prepared polyurethane material, but the polyurethane material prepared by polyester polyol containing side groups is selected, and the mechanical property of the material is greatly reduced due to the introduction of a branched chain in a molecular chain, so that the application range of the material is limited; the polyurethane material prepared by compounding the polyadipate-polyether copolyol or the polyadipate and the polyether has low mechanical strength and limited improvement on the humidity-resistant and heat-resistant aging performance due to large difference of polarity of the polyester and the polyether molecules and poor compatibility, and simultaneously, the forming process is more complicated and is not beneficial to production operation due to large viscosity of the prepolymer.
For example, chinese patent application CN1982351A discloses a method for preparing NDI-based microporous polyurethane elastomer, which selects single polyester polyol containing side groups, and although the hydrophobicity of the polyester polyol is improved to a certain extent, the side groups are introduced into the molecular chain, which greatly increases the distance between molecules, reduces the acting force between molecules, and causes the mechanical properties and heat resistance to be obviously reduced, the maximum tensile strength is only 4.78MPa, and the application range is limited.
The Chinese patent application CN104650330A discloses a preparation method of polyester diol and microporous polyurethane elastomer, the method selects mixed dihydric alcohol and dibasic acid to prepare polyester polyol with the molecular weight Mn of 500-4000, wherein the mixed dihydric alcohol is mixed by diol with ether bond, lateral methyl and straight chain, the prepared polyester polyol is synthesized with NDI at 120-140 ℃ to form prepolymer, and the prepolymer is reacted with chain extender components to prepare the microporous elastomer, similar to the Chinese patent application CN1982351A, the introduction of lateral group and/or ether bond reduces the mechanical property, heat resistance, oil resistance and the like of the material, the tensile strength is only 4.6MPa, the wet-heat aging property after 30 days (720h) of placement is only measured, and the water-resistant stability after 1000h of placement is uncertain.
Chinese patent application CN105504212A discloses a preparation method of a moisture-heat aging resistant polyurethane elastomer, the method selects polyester and polyether polytetrahydrofuran polyol to compound and prepare a co-block copolymerization polyurethane elastomer, the moisture-heat aging property is not ideal, the change rate of tensile strength under the condition of 40 ℃/93% RH/7d reaches 30%, the polyester and polyether have poor compatibility, the prepared prepolymer has high viscosity, the aromatic isocyanate and aliphatic isocyanate are compounded, although a certain viscosity is reduced, the reaction speed of the two isocyanates is different, the polyol has poor compatibility and is easy to tear, and the mechanical property, the dynamic property and the preparation process of the material are poor.
Disclosure of Invention
The invention aims to solve the technical problems that the defects and the defects mentioned in the background technology are overcome, the NDI-based polyurethane microporous elastomer with the moisture and heat aging resistance is provided, the NDI-based polyurethane microporous elastomer has excellent moisture and heat aging resistance, low-temperature flexibility, hydrolysis resistance stability and mechanical strength, and the preparation method of the NDI-based polyurethane microporous elastomer with the moisture and heat aging resistance is also provided.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the NDI-based polyurethane microporous elastomer is prepared from a component A and a component B according to the mass ratio of 100: (2.3-9.6), wherein the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
the moisture-heat aging resistant NDI-based polyurethane microporous elastomer disclosed by the invention has the advantages that the types and the addition proportions of the raw materials are reasonably designed, and the addition proportions of the components are controlled within the range of the invention, so that the polyurethane microporous elastomer is ensured to have excellent moisture-heat aging resistant performance and low-temperature flexibility, and the mechanical strength and hydrolysis resistance of the polyurethane microporous elastomer are improved. If the weight part of the polycarbonate modified polycaprolactone polyol is lower than the range of the invention, the wet heat aging performance of the polyurethane microporous elastomer is deteriorated, and if the weight part of the polycarbonate modified polycaprolactone polyol is beyond the range of the invention, the low-temperature flexibility of the polyurethane microporous elastomer cannot be ensured; if the weight part of the polyester polyol is less than the range of the invention, the mechanical properties of the obtained polyurethane microporous elastomer are not ideal, and if the weight part of the polyester polyol is beyond the range of the invention, the wet heat aging resistance of the obtained polyurethane microporous elastomer is reduced; if the weight part of the bio-based polyol is lower than the range of the invention, the wet heat aging resistance of the obtained polyurethane microporous elastomer is reduced, meanwhile, the viscosity is increased, the construction performance is influenced, and if the weight part of the bio-based polyol is beyond the range of the invention, the mechanical performance of the obtained polyurethane microporous elastomer is greatly reduced; NDI, a chain extender and a cross-linking agent are taken as molecular chain hard segments, and the weight parts of the NDI, the chain extender and the cross-linking agent are controlled within the range of the invention, so that the mechanical property of the microporous polyurethane elastomer can be improved, and the flexibility of the microporous polyurethane elastomer can be ensured; if the weight part of the catalyst is lower than the range of the invention, the reaction time is longer, the production efficiency is influenced, and if the weight part of the catalyst is beyond the range of the invention, the reaction rate is too fast, the operation time from pouring to die assembly is too short, even the operation is too late, and the appearance defects of the product are more; foam stabilizerThe addition of the (B) can ensure that the sizes of the foam holes of the polyurethane material are uniform, if the weight part of the (B) is lower than the range of the invention, the stability of foam air holes is poor, and foam collapse can be caused, and if the weight part of the (B) exceeds the range of the invention, the foam holes are too stable, no hole is formed, and shrinkage can be caused; the foaming agent is controlled within the range of the invention, and the density of the polyurethane material can be controlled within 400-600 kg/m3And meets the requirements of industrial application.
Preferably, the polycarbonate-modified polycaprolactone polyol is a copolyol prepared by taking polycarbonate as an initiator and opening caprolactone, and the molecular structural formula of the copolyol is shown as the formula (1):
the number average molecular weight of the polycarbonate modified polycaprolactone polyol is Mn 1000-3000, and the average functionality is 2-3.
The modified polycaprolactone is a polycarbonate/polycaprolactone block copolymer, and the crystallinity of the polycaprolactone molecular chain is destroyed by introducing the polycarbonate molecular chain, the modified polycaprolactone is liquid at room temperature, the operation is easy, the process flow in the preparation of the prepolymer is simplified, the energy consumption for melting the polyol at high temperature is saved, and the efficiency is improved. In addition, the single polycarbonate has poor low-temperature flexibility and optimal wet-heat aging resistance, the polycaprolactone molecular chain contains ether bonds, the low-temperature performance is good, and the polycarbonate modified polycaprolactone polyol is utilized, so that the wet-heat aging resistance of the microporous elastomer is improved, and meanwhile, the microporous elastomer has certain low-temperature flexibility.
Preferably, the polyester polyol is adipic acid polyester polyol with branching or side groups, specifically at least one of poly (ethylene glycol-trimethylolpropane-1, 4-butanediol adipate), poly (3-methyl-1, 5-pentanediol-1, 4-butanediol adipate) and poly (adipic acid) -3-methyl-1, 5-pentanediol-trimethylolpropane ester polyol; the number average molecular weight of the polyester polyol is 1000-6000, and the average functionality is 2-3. Because of the existence of the branched chain or the side group, the polyester polyol selected by the invention has low crystallinity, compared with the common adipic acid polyester, the prepared microporous elastomer has better flexibility and hydrolysis resistance, and does not need to be melted at high temperature before use, thereby saving energy consumption.
Preferably, the bio-based polyol is soybean oil polyol and/or dimer polyol, the number average molecular weight of the bio-based polyol is 400-3000, and the average functionality of the bio-based polyol is 2-3. The bio-based polyol selected by the invention has long carbon chain, does not contain ester group, has high hydrophobicity, has no ether bond in a molecular skeleton, has thermal degradation resistance compared with polyether, and can obviously improve the wet and heat aging performance of the microporous elastomer; the conventional mechanical property of the single-use bio-based polyol is poor, and the bio-based polyol and the polyester polyol are used together, so that the mechanical property is ensured, the damp-heat aging resistance is improved, the viscosity of the prepolymer is reduced due to the low viscosity of the bio-based polyol, and the stability and the efficiency of the forming process for preparing the polyurethane microporous elastomer are improved.
Preferably, the crosslinking agent is trifunctional polycaprolactone polyol taking trimethylolpropane as an initiator, and the molecular structural formula of the trifunctional polycaprolactone polyol is shown in formula (2):
the number average molecular weight of the cross-linking agent is Mn 240-540. The molecular chain of the prepared polyurethane microporous elastomer has a certain crosslinking degree by adopting the small molecular weight polycaprolactone as a crosslinking agent, a three-dimensional network structure is formed, the chain length is shortened, the migration of moisture is prevented, the damp-heat aging performance is improved, the compression permanent deformation of the material is reduced, and compared with other trifunctional crosslinking agents, the polycaprolactone contains ether bonds, so that the flexibility of the material is improved.
Preferably, the polymerization inhibitor is at least one of acetyl chloride, paranitrobenzoyl chloride, phosphoric acid and hydrochloric acid. Because NDI reaction activity is very high, the pH value of the polyalcohol can be adjusted by adding a polymerization inhibitor, the reaction speed during preparation of the prepolymer is controlled, and rapid heat release gel is prevented, so that the storage time of the prepolymer is prolonged.
Preferably, the chain extender is at least one of ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1,6 hexanediol and hydroquinone dihydroxyethyl ether; more preferably, the chain extender is at least one of diethylene glycol, 1, 3-butanediol and 1, 4-butanediol.
Preferably, the catalyst is a combination of a tertiary amine catalyst and an organic metal catalyst, the tertiary amine catalyst is at least one of triethylene diamine, bis (dimethylaminoethyl) ether, dimethyl ethanolamine and N, N-dimethyl N-octylamine, and the organic metal catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfide), zinc isooctoate and bismuth isooctanoate.
Preferably, the foam stabilizer is a nonionic foam stabilizer. Compared with the ionic foam stabilizer, the non-ionic foam stabilizer has high hydrophobicity and is not easy to decompose when meeting water; more preferably, the organic silicon surfactant is selected as the foam stabilizer, the emulsifying effect is good, the solubilizing effect on different components is strong, and the aperture ratio and the tolerance of the adjustable material are high.
Preferably, the foaming agent is water.
As a general inventive concept, the present invention also provides a method for preparing the wet heat aging resistant NDI-based polyurethane microcellular elastomer, comprising the steps of:
(1) preparing a component A: adding the measured polycarbonate modified polycaprolactone polyol, polyester polyol and bio-based polyol into a reaction kettle, uniformly mixing, dehydrating, adding a polymerization inhibitor, continuously heating, adding excessive diisocyanate, reacting to obtain a component A (namely an NCO-terminated prepolymer, wherein the NCO value of the prepolymer is 2-8%) after the reaction is finished, and sealing and storing for later use;
preparing a component B: uniformly mixing the measured cross-linking agent, chain extender, catalyst, foam stabilizer and foaming agent to obtain a component B;
(2) respectively adding the component A and the component B into a casting machine, wherein the mass ratio of the component A to the component B is 100: (2.3-9.6) pouring, injecting into a mold, curing and molding, demolding, cooling and obtaining an NDI-based polyurethane microporous elastomer semi-finished product;
(3) and curing and placing the semi-finished product to obtain the NDI-based polyurethane microporous elastomer.
In the preparation method, preferably, in the step (1), when the component A is prepared, the reaction kettle is preheated for 30-60 min at the temperature of 60-80 ℃, and then the raw materials are added; dehydrating in a vacuum environment, wherein the vacuum degree is 0.93-0.98 MPa, the dehydrating temperature is 112-118 ℃, and the dehydrating time is 2-3 h; and adding a polymerization inhibitor, heating to 123-150 ℃, adding diisocyanate, reacting for 30-60 min, and cooling after the reaction is finished to obtain the component A. When the component A is prepared, the dehydration parameters need to be controlled within the range of the invention, otherwise, the dehydration may be incomplete, and the diisocyanate added subsequently is easy to react with water to cause deterioration.
Preferably, in the step (2), the temperatures of the component A and the component B in the casting machine are controlled to be 60-110 ℃ and 30-60 ℃ respectively, the casting is performed after the flow and the temperature are stabilized for 1-2 hours in a circulating manner, the temperature of a mold is 70-120 ℃, the temperature of curing molding is 80-120 ℃, and the time is 15-60 min;
in the step (3), the curing temperature is 90-120 ℃, the curing time is 12-24 hours, and the mixture is placed at room temperature for 7-14 days after curing.
The invention mainly improves the humidity resistance, heat resistance and aging resistance of the NDI-based polyurethane microporous elastomer through the following three aspects: (1) polycarbonate modified polycaprolactone polyol is selected, and the polycarbonate polyol has more excellent moisture resistance and aging resistance and can enhance the wet heat aging performance of the material; (2) the biological polyol is used together with the liquid adipic acid polyester polyol, compared with other polyester polyols, the biological polyol has better flexibility, lower hygroscopicity and high hydrophobicity, and compared with polyether soft segment, no ether bond exists in a molecular skeleton, and the biological polyol has thermal degradation resistance; (3) the small molecular weight trifunctional polycaprolactone polyol is used for replacing part of small-weight dihydric alcohol to serve as a cross-linking agent, so that a polyurethane molecular chain has a certain cross-linking degree, a three-dimensional network structure is formed, the chain length is shortened, water molecules are not easy to permeate, ether bonds are introduced, and the wet heat aging performance is obviously improved. The NDI-based polyurethane microporous elastomer meets the industrial application requirements that the change rates of the tensile strength and the elongation at break are respectively less than or equal to 25% and less than or equal to 15% under the wet-heat condition of 70 ℃/95% RH/1000 h.
In the traditional process, polyester polyol containing side groups or polyether and polyester polyol are generally selected to be compounded to improve the stability against hydrolysis, but the mechanical properties of the material are reduced, and the application range of the product is limited. The polycarbonate modified polycaprolactone polyol and the polyester polyol are used together with the bio-based polyol, the intermolecular cohesive energy of the polycarbonate modified polycaprolactone polyol and the polyester polyol is large, the bio-based polyol has high hydrophobicity, the three polyols have good compatibility, and the high mechanical strength is ensured. The NDI-based polyurethane microporous elastomer meets the requirement that the material density is 400-600 kg/m3The tensile strength is more than or equal to 5.8MPa, and the elongation at break is more than or equal to 400 percent.
The invention also effectively solves the problems of complex process, high energy consumption and the like of preparing the NDI-based polyurethane microporous elastomer with the characteristics of heat and humidity resistance and aging resistance in the prior art. In the traditional process, the selected polycaprolactone is solid at room temperature, the moisture-heat-aging resistance of polyester polyol is not ideal, the mechanical strength of polyether polyol is too low, the process for processing the polyurethane microporous elastomer is complex, the efficiency is low, and the mechanical strength of the obtained product is low. The polycarbonate modified polycaprolactone polyol is selected, the regularity of the polycaprolactone molecular chain is destroyed by introducing the polycarbonate molecular chain, the crystallinity of the molecular chain is effectively reduced, the molecular chain is liquid at room temperature, and other added polyols are also liquid at room temperature, so that the process flow for preparing the NCO-terminated prepolymer is simplified, the polyol does not need to be subjected to melting pretreatment, the energy consumption is reduced, and the viscosity of the prepolymer is reduced by adding the bio-based polyol, so that the forming process for preparing the microporous elastomer is more stable and has high efficiency.
Compared with the prior art, the invention has the advantages that:
(1) the moisture-heat-aging-resistant NDI-based polyurethane microporous elastomer has excellent moisture-heat-aging-resistant performance, good hydrolysis resistance, low-temperature flexibility and good physical and mechanical properties, and has a density of 400-600 kg/m3The tensile strength is more than or equal to 5.8MPa, the elongation at break is more than or equal to 400 percent, the change rate of the tensile strength is less than or equal to 25 percent under the damp-heat condition of 70 ℃/95 percent RH/1000h, the elongation at break is less than or equal to 15 percent, and the use requirements under severe weather conditions such as high temperature, high humidity and the like can be completely met.
(2) In the process of preparing the NCO-terminated prepolymer, because NDI has high activity, high reaction speed and large and sharp heat release, the invention slows down the reaction speed by adding the polymerization inhibitor, avoids the gel deterioration of the prepolymer in the reaction process and effectively improves the stability of the prepared NCO-terminated prepolymer.
(3) The preparation method has the advantages of short process flow, simple operation, low process cost and high production efficiency, and is suitable for industrial production.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the NDI-based polyurethane microporous elastomer is prepared by reacting a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
60 parts of polycarbonate modified polycaprolactone diol with the average functionality of 2, the number average molecular weight of 2000 and the molecular structural formula shown in the formula (1);
30 parts of poly (ethylene adipate-glycol-trimethylolpropane-1, 4-butanediol ester glycol) with the average functionality of 2 and the number average molecular weight of 2000;
10 parts of dimer polyester diol with the average functionality of 2 and the number average molecular weight of 1000;
0.012 part of phosphoric acid;
NDI31.2 parts;
the component B comprises the following raw materials in parts by weight:
2.5 parts of 1, 4-butanediol;
1.5 parts of polycaprolactone triol with the average functionality of 3, the number average molecular weight of 240, the molecular structural formula shown in formula (2) and trimethylolpropane as an initiator;
0.06 part of a catalyst consisting of 0.04 part of Dabco33-LV (American Airy chemical), 0.015 part of dimethylethanolamine, 0.005 part of dibutyltin dilaurate;
l1501 (Meyer Corp., USA) foam stabilizer 0.8 parts;
0.64 part of water;
the NDI-based polyurethane microporous elastomer is prepared from a component A and a component B in a mass ratio of A: mixing B as 100: 5.5;
wherein, formula (1) is:
the formula (2) is:
the preparation method of the NDI-based polyurethane microcellular elastomer of this embodiment comprises the following steps:
(1) preparing a component A: preheating a reaction kettle at 80 ℃ for 30min, adding 60 parts of polycarbonate modified polycaprolactone diol (average functionality is 2 and number average molecular weight is 2000), 30 parts of poly adipic acid-ethylene glycol-trimethylolpropane-1, 4-butanediol ester diol (average functionality is 2 and number average molecular weight is 2000) and 10 parts of dimer polyester diol (average functionality is 2 and number average molecular weight is 1000) into the reaction kettle, uniformly mixing, dehydrating, and performing dehydration in a vacuum environment at the vacuum degree of 0.98MPa and the dehydration temperature of 118 ℃ for 2 h; then adding 0.012 part of phosphoric acid, raising the temperature to 145 ℃, adding 31.2 parts of NDI, reacting for 60min, measuring the NCO content to be 5.96% of the designed value, cooling after the reaction is finished to obtain a component A, and sealing and storing for later use;
preparing a component B: 2.5 parts of 1, 4-butanediol, 1.5 parts of polycaprolactone triol (average functionality of 3 and number average molecular weight of 240) using trimethylolpropane as an initiator, 0.06 part of a catalyst (consisting of 0.04 part of Dabco33-LV (American Aikochem), 0.015 part of dimethylethanolamine and 0.005 part of dibutyltin dilaurate), 0.8 part of L1501 (American Megaku corporation) foam stabilizer and 0.64 part of water were mixed uniformly to prepare a component B.
(2) Respectively adding the component A and the component B into a casting machine, controlling the temperature of the component A and the temperature of the component B in the casting machine to be 110 ℃ and 50 ℃, circulating for 1h, and after the flow and the temperature are stable, according to the mass ratio of the component A to the component B being 100: and 5.5, pouring at the mold temperature of 120 ℃ and the curing molding temperature of 120 ℃ for 15min, demolding after curing molding, and cooling to obtain the NDI-based polyurethane microporous elastomer semi-finished product.
(3) And curing the semi-finished product at 120 ℃ for 12h, and standing at room temperature for 7d to obtain the NDI-based polyurethane microporous elastomer.
Example 2:
the NDI-based polyurethane microporous elastomer is prepared by reacting a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
70 parts of polycarbonate modified polycaprolactone diol with the average functionality of 2, the number average molecular weight of 2000 and the molecular structural formula shown in the formula (1);
15 parts of poly (ethylene adipate-glycol-trimethylolpropane-1, 4-butanediol ester glycol) with the average functionality of 2 and the number average molecular weight of 2000;
15 parts of dimer polyester diol with the average functionality of 2 and the number average molecular weight of 1000;
0.012 part of phosphoric acid;
NDI33.8 parts;
the component B comprises the following raw materials in parts by weight:
4.3 parts of 1, 6-hexanediol;
2.2 parts of polycaprolactone triol with the average functionality of 3, the number average molecular weight of 240, the molecular structural formula shown in formula (2) and trimethylolpropane as an initiator;
0.06 part of a catalyst consisting of 0.04 part of Dabco33-LV (American Airy chemical), 0.015 part of dimethylethanolamine, 0.005 part of dibutyltin dilaurate;
l1501 (Meyer Corp., USA) foam stabilizer 0.8 parts;
0.64 part of water;
the NDI-based polyurethane microporous elastomer is prepared from a component A and a component B in a mass ratio of A: mixing B as 100: 8.0;
wherein, formula (1) is:
the formula (2) is:
the preparation method of the NDI-based polyurethane microcellular elastomer of this embodiment comprises the following steps:
(1) preparing a component A: preheating a reaction kettle at 80 ℃ for 30min, adding 70 parts of polycarbonate modified polycaprolactone diol (average functionality is 2 and number average molecular weight is 2000), 15 parts of poly adipic acid-ethylene glycol-trimethylolpropane-1, 4-butanediol ester diol (average functionality is 2 and number average molecular weight is 2000) and 15 parts of dimer polyester diol (average functionality is 2 and number average molecular weight is 1000) into the reaction kettle, uniformly mixing, dehydrating, and performing dehydration in a vacuum environment at the vacuum degree of 0.98MPa and the dehydration temperature of 118 ℃ for 2 h; then adding 0.012 part of phosphoric acid, raising the temperature to 145 ℃, adding 33.8 parts of NDI, reacting for 60min, measuring the NCO content to be 6.48% of the designed value, cooling after the reaction is finished to obtain a component A, and sealing and storing for later use;
preparing a component B: 4.3 parts of 1, 6-hexanediol, 2.2 parts of polycaprolactone triol (average functionality of 3, number average molecular weight 240) using trimethylolpropane as an initiator, 0.06 part of a catalyst (composed of 0.04 part of Dabco33-LV (American Aikochem), 0.015 part of dimethylethanolamine, 0.005 part of dibutyltin dilaurate), 0.8 part of L1501 (American Meiji Co.) foam stabilizer, and 0.64 part of water were mixed uniformly to prepare a component B.
(2) Respectively adding the component A and the component B into a casting machine, controlling the temperature of the component A and the temperature of the component B in the casting machine to be 110 ℃ and 50 ℃, circulating for 1h, and after the flow and the temperature are stable, according to the mass ratio of the component A to the component B being 100:8.0, pouring, wherein the temperature of a mold is 120 ℃, the curing and forming temperature is 120 ℃, the time is 15min, demolding after curing and forming, cooling and obtaining the NDI-based polyurethane microporous elastomer semi-finished product.
(3) And curing the semi-finished product at 120 ℃ for 12h, and standing at room temperature for 7d to obtain the NDI-based polyurethane microporous elastomer.
Example 3:
the NDI-based polyurethane microporous elastomer is prepared by reacting a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
79.5 parts of polycarbonate modified polycaprolactone diol with the average functionality of 2, the number average molecular weight of 2000 and the molecular structural formula shown as the formula (1);
15.5 parts of poly (3-methyl-1, 5-pentanediol-1, 4-butanediol adipate) glycol with the average functionality of 2 and the number average molecular weight of 2000;
5 parts of dimer polyester diol with the average functionality of 2 and the number average molecular weight of 1000;
0.012 part of phosphoric acid;
NDI26.9 parts;
the component B comprises the following raw materials in parts by weight:
1.5 parts of 1, 4-butanediol;
1.0 part of polycaprolactone triol with average functionality of 3, number average molecular weight of 240, molecular structural formula shown in formula (2) and trimethylolpropane as initiator;
0.06 part of a catalyst consisting of 0.04 part of Dabco33-LV (American Airy chemical), 0.015 part of dimethylethanolamine, 0.005 part of dibutyltin dilaurate;
l1501 (Meyer Corp., USA) foam stabilizer 0.8 parts;
0.64 part of water;
the NDI-based polyurethane microporous elastomer is prepared from a component A and a component B in a mass ratio of A: mixing B as 100: 4.0;
wherein, formula (1) is:
the formula (2) is:
the preparation method of the NDI-based polyurethane microcellular elastomer of this embodiment comprises the following steps:
(1) preparing a component A: preheating a reaction kettle at 80 ℃ for 30min, adding 79.5 parts of polycarbonate modified polycaprolactone diol (with average functionality of 2 and number average molecular weight of 2000), 15.5 parts of poly adipic acid-3-methyl-1, 5-pentanediol-1, 4-butanediol diol (with average functionality of 2 and number average molecular weight of 2000) and 5 parts of dimer polyester diol (with average functionality of 2 and number average molecular weight of 1000) into the reaction kettle, uniformly mixing, dehydrating, wherein the dehydration is carried out in a vacuum environment, the vacuum degree is 0.98MPa, the dehydration temperature is 118 ℃, and the time is 2 h; then adding 0.012 part of phosphoric acid, raising the temperature to 145 ℃, adding 26.9 parts of NDI, reacting for 60min, measuring the NCO content to be 4.51% of the designed value, cooling after the reaction is finished to obtain a component A, and sealing and storing for later use;
preparing a component B: 1.5 parts of 1, 4-butanediol, 1.0 part of polycaprolactone triol (average functionality of 3 and number average molecular weight of 240) using trimethylolpropane as an initiator, 0.06 part of catalyst (consisting of 0.04 part of Dabco33-LV (American Aikochem), 0.015 part of dimethylethanolamine and 0.005 part of dibutyltin dilaurate), 0.8 part of L1501 (American Megaku corporation) foam stabilizer and 0.64 part of water were mixed uniformly to prepare a component B.
(2) Respectively adding the component A and the component B into a casting machine, controlling the temperature of the component A and the temperature of the component B in the casting machine to be 110 ℃ and 50 ℃, circulating for 1h, and after the flow and the temperature are stable, according to the mass ratio of the component A to the component B being 100:4.0, pouring, wherein the temperature of the mold is 120 ℃, the curing and forming temperature is 120 ℃, the time is 15min, demolding after curing and forming, cooling and obtaining the NDI-based polyurethane microporous elastomer semi-finished product.
(3) And curing the semi-finished product at 120 ℃ for 12h, and standing at room temperature for 7d to obtain the NDI-based polyurethane microporous elastomer.
Comparative example 1:
the NDI-based polyurethane microporous elastomer is prepared by reacting a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
55 parts of poly (3-methyl-1, 5-pentanediol-1, 4-butanediol adipate) glycol with the average functionality of 2 and the number average molecular weight of 2000;
35 parts of poly (ethylene adipate-glycol-trimethylolpropane-1, 4-butanediol ester glycol) with the average functionality of 2 and the number average molecular weight of 2000;
10 parts of dimer polyester diol with the average functionality of 2 and the number average molecular weight of 1000;
0.012 part of phosphoric acid;
NDI 29.3 parts;
the component B comprises the following raw materials in parts by weight:
1.7 parts of 1, 4-butanediol;
1.8 parts of polycaprolactone triol with the average functionality of 3, the number average molecular weight of 240, the molecular structural formula shown in formula (2) and trimethylolpropane as an initiator;
0.06 part of a catalyst consisting of 0.04 part of Dabco33-LV (American Airy chemical), 0.015 part of dimethylethanolamine, 0.005 part of dibutyltin dilaurate;
l1501 (Meyer Corp., USA) foam stabilizer 0.8 parts;
0.64 part of water;
the NDI-based polyurethane microporous elastomer is prepared from a component A and a component B in a mass ratio of A: mixing B as 100: 5.0;
wherein, formula (2) is:
the preparation method of the NDI-based polyurethane microcellular elastomer of the present comparative example comprises the steps of:
(1) preparing a component A: preheating a reaction kettle at 80 ℃ for 30min, adding 55 parts of poly adipic acid-3-methyl-1, 5-pentanediol-1, 4-butanediol ester diol (average functionality is 2 and number average molecular weight is 2000), 35 parts of poly adipic acid-ethylene glycol-trimethylolpropane-1, 4-butanediol ester diol (average functionality is 2 and number average molecular weight is 2000) and 10 parts of dimer polyester diol (average functionality is 2 and number average molecular weight is 1000) into the reaction kettle, uniformly mixing, dehydrating, and dehydrating under a vacuum environment, wherein the vacuum degree is 0.98MPa, the dehydration temperature is 118 ℃, and the time is 2 h; adding 0.012 part of phosphoric acid, raising the temperature to 145 ℃, adding 29.3 parts of NDI, reacting for 60min, measuring the NCO content to be 5.52 percent of the designed value, cooling to obtain the component A after the reaction is finished, and sealing and storing for later use.
Preparing a component B: 1.7 parts of 1, 4-butanediol, 1.8 parts of polycaprolactone triol (average functionality of 3 and number average molecular weight of 240) using trimethylolpropane as an initiator, 0.06 part of a catalyst (consisting of 0.04 part of Dabco33-LV (American Aikochem), 0.015 part of dimethylethanolamine and 0.005 part of dibutyltin dilaurate), 0.8 part of L1501 (American Megaku corporation) foam stabilizer and 0.64 part of water were mixed uniformly to prepare a component B.
(2) Respectively adding the component A and the component B into a casting machine, controlling the temperature of the component A and the temperature of the component B in the casting machine to be 110 ℃ and 50 ℃, circulating for 1h, and after the flow and the temperature are stable, according to the mass ratio of the component A to the component B being 100: and 5.0, pouring at the mold temperature of 120 ℃ for 15min, curing and forming at the temperature of 120 ℃, demolding after curing and forming, and cooling to obtain the NDI-based polyurethane microporous elastomer semi-finished product.
(3) And curing the semi-finished product at 120 ℃ for 12h, and standing at room temperature for 7d to obtain the NDI-based polyurethane microporous elastomer.
Comparative example 2:
the NDI-based polyurethane microporous elastomer is prepared by reacting a component A and a component B, wherein the component A comprises the following raw materials in parts by weight:
50 parts of polycarbonate diol having an average functionality of 2 and a number average molecular weight of 2000;
38 parts of poly (ethylene adipate-glycol-trimethylolpropane-1, 4-butanediol glycol) with the average functionality of 2 and the number average molecular weight of 2000;
12 parts of dimer polyester diol with the average functionality of 2 and the number average molecular weight of 1000;
0.012 part of phosphoric acid;
NDI31.5 parts;
the component B comprises the following raw materials in parts by weight:
4.3 parts of 1, 6-hexanediol;
1.2 parts of polycaprolactone triol with average functionality of 3, number average molecular weight of 240, molecular structural formula shown in formula (2) and trimethylolpropane as initiator
0.06 part of a catalyst consisting of 0.04 part of Dabco33-LV (American Airy chemical), 0.015 part of dimethylethanolamine, 0.005 part of dibutyltin dilaurate;
l1501 (Meyer Corp., USA) foam stabilizer 0.8 parts;
0.64 part of water;
the NDI-based polyurethane microporous elastomer is prepared from a component A and a component B in a mass ratio of A: mixing B as 100: 7.0;
wherein, formula (2) is:
the preparation method of the NDI-based polyurethane microcellular elastomer of the present comparative example comprises the steps of:
(1) preparing a component A: preheating a reaction kettle at 80 ℃ for 30min, adding 50 parts of polycarbonate diol (average functionality is 2 and number average molecular weight is 2000), 38 parts of poly adipic acid-ethylene glycol-trimethylolpropane-1, 4-butanediol ester diol (average functionality is 2 and number average molecular weight is 2000) and 12 parts of dimer polyester diol (average functionality is 2 and number average molecular weight is 1000) into the reaction kettle, uniformly mixing, and dehydrating, wherein the dehydration is carried out in a vacuum environment, the vacuum degree is 0.98MPa, the dehydration temperature is 118 ℃, and the time is 2 hours; adding 0.012 part of phosphoric acid, raising the temperature to 145 ℃, adding 31.5 parts of NDI, reacting for 60min, measuring the NCO content to be 6.02 percent of the designed value, cooling to obtain the component A after the reaction is finished, and sealing and storing for later use.
Preparing a component B: 4.3 parts of 1, 6-hexanediol, 1.2 parts of polycaprolactone triol (average functionality of 3, number average molecular weight 240) using trimethylolpropane as an initiator, 0.06 part of a catalyst (composed of 0.04 part of Dabco33-LV (American Aikochem), 0.015 part of dimethylethanolamine, 0.005 part of dibutyltin dilaurate), 0.8 part of L1501 (American Meiji Co.) foam stabilizer, and 0.64 part of water were mixed uniformly to prepare a component B.
(2) Respectively adding the component A and the component B into a casting machine, controlling the temperature of the component A and the temperature of the component B in the casting machine to be 110 ℃ and 50 ℃, circulating for 1h, and after the flow and the temperature are stable, according to the mass ratio of the component A to the component B being 100:7.0, pouring, wherein the temperature of a mold is 120 ℃, the temperature of curing molding is 120 ℃, the time is 15min, demolding after curing molding, cooling and obtaining the NDI-based polyurethane microporous elastomer semi-finished product.
(3) And curing the semi-finished product at 120 ℃ for 12h, and standing at room temperature for 7d to obtain the NDI-based polyurethane microporous elastomer.
The NDI-based polyurethane microcellular elastomers obtained in the above examples 1 to 3 and comparative examples 1 to 2 were tested for their associated properties, and the test results are shown in Table 1.
TABLE 1 relevant Properties of NDI-based polyurethane microcellular elastomers obtained in inventive examples 1-3 and comparative examples 1-2
As shown in Table 1, compared with comparative examples 1 and 2, the moisture-heat-aging-resistant NDI-based polyurethane microporous elastomer disclosed by the invention has excellent moisture-heat-aging-resistant performance, good low-temperature flexibility and good physical and mechanical properties, and the material density is 400-600 kg/m3Within the range, the tensile strength is more than or equal to 5.8MPa, the elongation at break is more than or equal to 400 percent, the change rate of the tensile strength is less than or equal to 25 percent under the condition of 70 ℃/95 percent RH/1000h of damp-heat aging, the elongation at break is less than or equal to 15 percent, and the use requirements under severe weather conditions such as high temperature, high humidity and the like can be completely met.
Claims (6)
1. The NDI-based polyurethane microporous elastomer is characterized by comprising a component A and a component B according to the mass ratio of 100: (2.3-9.6), wherein the component A comprises the following raw materials in parts by weight:
60-79.5 parts of polycarbonate modified polycaprolactone polyol,
10.5-32 parts of polyester polyol,
5-15 parts of bio-based polyol,
0.008 to 0.015 part of polymerization inhibitor,
16.3-38 parts of diisocyanate NDI;
the component B comprises the following raw materials in parts by weight:
1.3-5.9 parts of chain extender,
0.5 to 2.3 parts of a crosslinking agent,
0.01 to 0.07 part of catalyst,
0.2 to 1.0 part of foam stabilizer,
0.2-0.8 part of foaming agent;
the polycarbonate modified polycaprolactone polyol is copolymerized polyol prepared by taking polycarbonate as an initiator and opening a ring of caprolactone; the number average molecular weight of the polycarbonate modified polycaprolactone polyol is Mn = 1000-3000, and the average functionality is 2-3;
the polyester polyol is branched or has lateral group adipic acid polyester polyol, and the branched or lateral group adipic acid polyester polyol is at least one of poly adipic acid-ethylene glycol-trimethylolpropane-1, 4-butanediol ester, poly adipic acid-3-methyl-1, 5-pentanediol-1, 4-butanediol ester, and poly adipic acid-3-methyl-1, 5-pentanediol-trimethylolpropane ester polyol; the number average molecular weight of the polyester polyol is Mn = 1000-6000, and the average functionality is 2-3;
the bio-based polyol is soybean oil polyol and/or dimer polyol, the number average molecular weight of the bio-based polyol is Mn = 400-3000, and the average functionality of the bio-based polyol is 2-3;
the cross-linking agent is tri-functionality polycaprolactone polyol taking trimethylolpropane as an initiator; the number average molecular weight of the cross-linking agent is Mn = 240-540.
2. The wet heat aging resistant NDI-based polyurethane microcellular elastomer according to claim 1, wherein said polymerization inhibitor is at least one of acetyl chloride, paranitrobenzoyl chloride, phosphoric acid, and hydrochloric acid.
3. The wet heat aging resistant NDI-based polyurethane microcellular elastomer according to claim 1, wherein the chain extender is at least one of ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, hydroquinone bis hydroxyethyl ether;
the catalyst is compounded by a tertiary amine catalyst and an organic metal catalyst, the tertiary amine catalyst is at least one of triethylene diamine, bis (dimethylaminoethyl) ether, dimethylethanolamine and N, N-dimethyl N-octylamine, and the organic metal catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur), zinc isooctoate and bismuth isooctanoate;
the foam stabilizer is a nonionic foam stabilizer.
4. A process for preparing a microcellular elastomer based on a moisture-and heat-aging-resistant NDI-based polyurethane according to any one of claims 1 to 3, comprising the steps of:
(1) preparing a component A: adding the measured polycarbonate modified polycaprolactone polyol, polyester polyol and bio-based polyol into a reaction kettle, uniformly mixing, dehydrating, adding a polymerization inhibitor, continuously heating, adding excessive diisocyanate NDI, reacting, and preparing a component A after the reaction is finished;
preparing a component B: uniformly mixing the measured cross-linking agent, chain extender, catalyst, foam stabilizer and foaming agent to obtain a component B;
(2) respectively adding the component A and the component B into a casting machine, wherein the mass ratio of the component A to the component B is 100: (2.3-9.6) pouring, injecting into a mold, curing and molding, and then demolding to obtain an NDI-based polyurethane microporous elastomer semi-finished product;
(3) and curing and placing the semi-finished product to obtain the NDI-based polyurethane microporous elastomer.
5. The preparation method according to claim 4, wherein in the step (1), when the component A is prepared, the reaction kettle is preheated at 60-80 ℃ for 30-60 min, and then the raw materials are added; dehydrating in a vacuum environment, wherein the vacuum degree is 0.93-0.98 MPa, the dehydrating temperature is 112-118 ℃, and the dehydrating time is 2-3 h; and adding a polymerization inhibitor, heating to 123-150 ℃, adding diisocyanate NDI, reacting for 30-60 min, and cooling after the reaction is finished to obtain the component A.
6. The preparation method according to claim 4 or 5, characterized in that in the step (2), the temperatures of the component A and the component B in the casting machine are controlled to be 60-110 ℃ and 30-60 ℃ respectively, the casting is carried out after the flow and the temperature are stabilized for 1-2 hours in a circulating manner, the temperature of a mold is 70-120 ℃, the temperature of curing and forming is 80-120 ℃, and the time is 15-60 min;
in the step (3), the curing temperature is 90-120 ℃, the curing time is 12-24 hours, and the mixture is placed at room temperature for 7-14 days after curing.
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