CN112961302B - High-temperature and high-humidity resistant polyurethane foam material - Google Patents
High-temperature and high-humidity resistant polyurethane foam material Download PDFInfo
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Abstract
The invention relates to a high-temperature and high-humidity resistant polyurethane foam material, which comprises the following steps: the method comprises the following steps of (1) selecting castor oil polyol with a hydrophobic structure as a base, and carrying out prepolymerization on one or more of MDI, TDI or IPDI, PTEMG and castor oil to obtain a hydroxyl component polymer polyol component A; preparing a prepolymer B component containing-NCO component; coating the component A and the component B on a coating machine according to a certain proportion, and curing for 4 hours in an oven at 80 ℃ to obtain the foam material prepared by the formula. The foaming material prepared by the invention has good compression permanent deformation performance and good compression stress attenuation.
Description
Technical Field
The invention relates to the field of foaming materials, and particularly relates to high-temperature and high-humidity resistant polyurethane foam and a preparation method thereof
Background
The polyurethane foam is a porous polymer which is generated by reacting isocyanate based on hydroxyl and contains-NHCOO-repeating structural units on the main chain, and is called PUF for short. The polyurethane foam has excellent energy absorption, buffering and heat insulation properties. The compression permanent deformation and the compression stress attenuation of the polyurethane foam are important indexes for evaluating the quality of the polyurethane foam, and can reflect the stable service life of the polyurethane foam under a specific working condition.
The existing foam cotton applied to the high-temperature and high-humidity environment is basically an organosilicon system, the organosilicon is more hydrolysis-resistant and high-temperature-resistant than polyurethane system foam cotton in characteristics, but the price is much higher than that of polyurethane system foam cotton, and the performance attenuation of the existing common polyurethane cotton in the environment of double 85 is very obvious, the main reason is that the structure of the existing common polyurethane cotton contains one or more of a large number of ester bonds, urea bonds and urethane groups, the groups generate hydrolysis and chain breakage of partial chain under the environment of 85, particularly, acid generated by hydrolysis of the ester groups can further promote hydrolysis to form vicious circle and accelerate the attenuation of the foam cotton performance, so that the common polyurethane is difficult to use under the environment of 85 for a long time, the mechanical performance is particularly obvious, such as tensile strength, compression stress, compression permanent deformation and other indexes, and the indexes can have great attenuation after 72 hours of double 85 aging.
Therefore, ten polyurethane foams resistant to the environment of double 85 are required to be developed.
Disclosure of Invention
In order to solve the technical problems, the invention can greatly reduce the mechanical property attenuation and the compression permanent deformation of the existing polyurethane foam under the environment of double 85.
The invention can approach organic silica gel foam under the condition of double 85, and simultaneously has higher tensile strength and tearing strength, lower cost advantage and lower heat conductivity coefficient.
The high-temperature and high-humidity resistant polyurethane foam material is characterized by comprising the following steps in parts by weight:
the preparation of the component A comprises the following steps:
s1: the method comprises the steps of selecting castor oil polyol with a hydrophobic structure as a base, and carrying out prepolymerization on one or more of MDI, TDI or IPDI, PTEMG and castor oil to obtain a hydroxyl component polymer polyol component I;
s2: placing 60-75 parts of the first component obtained in the step S1 into a container;
s3: adding 0.5-5.0 parts of hydrolysis resistant agent, 1.0-5.0 parts of hydrophobic nano silicon dioxide, 0.5-5 parts of foaming agent, 1.5-10 parts of silicone oil, 0.1-1.5 parts of antioxidant, 0.2-2.0 parts of light stabilizer, 2-10 parts of chain extender, 2-8 parts of cross-linking agent, 0.1-1 part of catalyst and 3-10 parts of black paste into a container;
s4: stirring the container at a high speed for 2min under a stirring machine of 2000 rpm to ensure uniform mixing to obtain a component A;
the preparation of the component B comprises the following steps:
s5: one or more of MDI, TDI or IPDI is subjected to heat preservation for 2 hours at the temperature of 60 ℃ to obtain a standby material;
s6: adding 400-600 parts of dehydrated castor oil into a reaction kettle, starting stirring and simultaneously heating to 40 ℃;
s7: adding 600-800 parts of the standby material in the step S5 into a stirring reaction kettle, heating to 50 ℃, and keeping for 30min;
s8: heating the reaction kettle to 60 ℃ and preserving the temperature for 1h;
s9: heating the temperature of the reaction kettle to 70 ℃ and preserving the temperature for 1h;
s10: heating the temperature of the reaction kettle to 80 ℃ and preserving the temperature for 2 hours;
through S8-S10, one or more of MDI, TDI or IPDI and dehydrated castor oil are fully reacted, molecular chains are increased, the molecular weight distribution of the obtained product is more uniform, and the mechanical property of the product is improved.
S11: cooling the temperature of the reaction kettle to 60 ℃, adding 78 parts of 2-methyl-1, 3-propylene glycol, and preserving the temperature for 1 hour;
s12: heating to 70 ℃, and keeping the temperature for 1h;
s13: heating to 80 ℃, and reacting for 2 hours in a heat preservation way;
through S12-S13, the molecular chain is further subjected to chain extension, the molecular weight is increased, and the number of methyl side chains in the molecular chain of the component B is increased, so that the hydrophobicity is properly increased.
S14: cooling to 40 ℃ and discharging to obtain a-NCO component prepolymer B component;
preparing a foaming material:
and (3) putting the component A and the component B into a container according to the weight part ratio of 3-5, stirring at a high speed for 15s under a stirrer rotating at a speed of 2500 rpm, coating on a coating machine, and curing the coated sample in an oven at 80 ℃ for 4 hours to obtain the foaming material.
Further, the specific steps of the component A are as follows:
s11: one or more of MDI, TDI or IPDI is subjected to heat preservation for 2 hours at the temperature of 60 ℃ to obtain a standby material;
s12: adding 60-80 parts of dehydrated castor oil and 20-40 parts of PTEMG into a reaction kettle, starting stirring and simultaneously heating to 40 ℃;
s13: 2-10 parts of the standby material prepared in the step S11 are added into a stirring reaction kettle, and the temperature is increased to 50 ℃ and is kept for 30min;
s14: heating the temperature of the reaction kettle to 60 ℃ and preserving the temperature for 1h;
s15: heating the temperature of the reaction kettle to 70 ℃ and preserving the temperature for 1h;
s16: and (3) heating the reaction kettle to 80 ℃, preserving the temperature for 3h, naturally cooling to 40 ℃, and discharging to obtain the hydroxyl component polymer polyol component I.
Further, the hydrolysis resistant agent is a carbodiimide modified polymer.
Further, the foaming agent is one or more of water, HCFC-141B, cyclopentane and the like.
Further, the silicone oil is 1-5 parts of silicone oil I, 0.5-5 parts of silicone oil II, and the silicone oil I and the silicone oil II are hydrolysis-resistant silicone oil, the silicone oil I is polysiloxane, and the silicone oil II is alkane block copolymer.
Further, the chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol and diethylene glycol.
Further, the crosslinking agent is one or more of glycerol, trimethylolpropane and polyether 310 (with the weight of 100 parts and the functionality of 3).
Further, the catalyst is one or more of A33, T9 and T12.
Furthermore, the thickness of the coating wet film is 0.38mm, and the release paper for the upper film and the 50umPET film for the lower film are used.
By the scheme, the invention at least has the following advantages:
(1) Comparison of compression set Properties
Ordinary polyurethane foam (unmodified prepolymerization, no hydrolysis-resistant stabilizer added) with density of 350kg/m 3 When the material is placed for 22 hours under the condition of 50% compression in a double 85 environment, the compression set is more than 20%, and after being placed for 168 hours, the material has 50% compression set, namely the material can not rebound completely; the density of a sample prepared by the modified formula of the invention is 350kg/m 3 When the material is placed under the condition of 70% compression for 22h under the double 85 environment, the compression permanent deformation is 1.18%, and after the material is placed for 168h, the material is compressed permanentlyThe long-term deformation is 2.69%, the compression set after placing for 500h is 6.54%, and the compression set performance is obviously improved.
(2) Compressive stress decay contrast
Ordinary polyurethane foam (unmodified prepolymerization, no hydrolysis-resistant stabilizer added) with density of 350kg/m 3 When the material is placed under a double 85 environment for 22 hours under the condition that the 50% compressive stress deflection force is 79kPa under the compression condition of 50%, the material recovers for 30min, the 50% compressive stress deflection force is 49kPa under the test, and the stress attenuation reaches 37.97%; after being placed in a double 85 environment for 168 hours under the condition of 50% compression, the material cannot rebound at all.
The density of the sample prepared by the modified formula of the invention is 350kg/m 3 When the composite material is placed under a double 85 environment under the condition of 50% of compression stress deflection force of 88kPa for 22 hours, the composite material is recovered for 30 minutes after being tested under the condition of 50% of compression stress deflection force of 81kPa, the stress attenuation reaches 7.95%, and after being placed under the double 85 environment under the condition of 50% of compression for 168 hours, the composite material is recovered for 30 minutes after being tested under the condition of 50% of compression stress deflection force of 74kPa, and the stress attenuation reaches 15.9%.
The foregoing is a summary of the present invention, and the following is a detailed description of the preferred embodiments of the present invention in order to provide a clear understanding of the technical features of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1:
the preparation of the component A comprises the following steps:
keeping the MDI at 60 ℃ for 2 hours to obtain a standby material; adding 60 parts of dehydrated castor oil and 20 parts of PTEMG into a reaction kettle, starting stirring and simultaneously heating to 40 ℃; adding 20 parts of standby materials into a stirring reaction kettle, heating to 50 ℃, and keeping for 30min; and (3) carrying out three-stage heating operation, heating the temperature of the reaction kettle to 60 ℃ and preserving heat for 1h, heating the temperature of the reaction kettle to 70 ℃ and preserving heat for 1h, heating the temperature of the reaction kettle to 80 ℃ and preserving heat for 3h, naturally cooling to 40 ℃ and discharging to obtain the hydroxyl component polymer polyol component I.
Placing 60 parts of the first component in a container; adding 0.5 part of carbodiimide-modified polymer, 1.0 part of hydrophobic nano-silica, 0.5 part of water, 0.5 part of polysiloxane, 1 part of alkane block copolymer, 0.1 part of antioxidant, 0.20 part of light stabilizer, 2 parts of glycol, 2 parts of glycerol, 0.1 part of catalyst A33 and 3 parts of black paste into a container;
stirring the container at a high speed for 2min under a stirring machine of 2000 rpm to ensure uniform mixing to obtain a component A;
the preparation of the component B comprises the following steps:
keeping the MDI at 60 ℃ for 2 hours to obtain a standby material; adding 400 parts of dehydrated castor oil into a reaction kettle, starting stirring and simultaneously heating to 40 ℃; adding 600 parts of standby materials into a stirring reaction kettle, heating to 50 ℃, and keeping for 30min; heating the temperature of the reaction kettle to 60 ℃ and preserving the temperature for 1h;
heating the temperature of the reaction kettle to 70 ℃ and preserving the temperature for 1h; heating the temperature of the reaction kettle to 80 ℃ and preserving the temperature for 2 hours; cooling the temperature of the reaction kettle to 60 ℃, adding 78 parts of 2-methyl-1, 3-propylene glycol, and preserving the temperature for 1 hour;
heating to 70 ℃, and keeping the temperature for 1h; heating to 80 ℃, and reacting for 2 hours under the condition of heat preservation; cooling to 40 ℃ and discharging to obtain the-NCO component prepolymer B component.
Preparing a foaming material:
and (3) putting the component A and the component B into a container according to the weight part ratio of 3, stirring at a high speed for 15s under a stirring machine of 2500 revolutions per minute, coating on a coating machine, and curing the coated sample in an oven at 80 ℃ for 4 hours to obtain the foaming material.
Example 2:
the component A is prepared by the following steps:
keeping the temperature of the mixture of MDI and TDI at 60 ℃ for 2 hours to obtain a standby material; adding 70 parts of dehydrated castor oil and 30 parts of PTEMG into a reaction kettle, starting stirring and simultaneously heating to 40 ℃; adding 5 parts of standby materials into a stirring reaction kettle, heating to 50 ℃, and keeping for 30min; and (3) carrying out three-stage heating operation, heating the temperature of the reaction kettle to 60 ℃ and preserving heat for 1h, heating the temperature of the reaction kettle to 70 ℃ and preserving heat for 1h, heating the temperature of the reaction kettle to 80 ℃ and preserving heat for 3h, naturally cooling to 40 ℃ and discharging to obtain the hydroxyl component polymer polyol component I.
Taking 65 parts of the first component and placing the first component in a container; adding 3 parts of carbodiimide modified polymer, 3 parts of hydrophobic nano silicon dioxide, 3 parts of foaming agent HCFC-141B, 2 parts of polysiloxane and 3 parts of alkane block copolymer, 1 part of antioxidant, 1 part of light stabilizer, 5 parts of propylene glycol, 4 parts of trimethylolpropane, 0.5 part of catalyst T9 and 5 parts of black paste into a container;
stirring the container at a high speed for 2min under a stirring machine of 2000 rpm to ensure uniform mixing to obtain a component A;
the preparation of the component B comprises the following steps:
keeping the temperature of MDI at 60 ℃ for 2 hours to obtain a standby material; adding 500 parts of dehydrated castor oil into a reaction kettle, starting stirring and simultaneously heating to 40 ℃; adding 700 parts of standby materials into a stirring reaction kettle, heating to 50 ℃, and keeping for 30min; heating the temperature of the reaction kettle to 60 ℃ and preserving the temperature for 1h;
heating the temperature of the reaction kettle to 70 ℃ and preserving the temperature for 1h; heating the reaction kettle to 80 ℃ and preserving the temperature for 2 hours; cooling the temperature of the reaction kettle to 60 ℃, adding 78 parts of 2-methyl-1, 3-propylene glycol, and preserving the temperature for 1 hour;
heating to 70 ℃, and keeping the temperature for 1h; heating to 80 ℃, and reacting for 2 hours in a heat preservation way; cooling to 40 ℃ and discharging to obtain the-NCO component prepolymer B component.
Preparing a foaming material:
the component A and the component B are placed into a container according to the weight part ratio of 1.
Example 3:
the preparation of the component A comprises the following steps:
the IPDI is kept at the temperature of 60 ℃ for 2 hours to obtain a standby material; adding 80 parts of dehydrated castor oil and 40 parts of PTEMG into a reaction kettle, starting stirring and simultaneously heating to 40 ℃; adding 10 parts of standby materials into a stirring reaction kettle, heating to 50 ℃, and keeping for 30min; and (3) carrying out three-stage heating operation, heating the temperature of the reaction kettle to 60 ℃ and preserving heat for 1h, heating the temperature of the reaction kettle to 70 ℃ and preserving heat for 1h, heating the temperature of the reaction kettle to 80 ℃ and preserving heat for 3h, naturally cooling to 40 ℃ and discharging to obtain the hydroxyl component polymer polyol component I.
Taking 75 parts of the first component and placing the first component in a container; adding 5.0 parts of carbodiimide modified polymer, 5.0 parts of hydrophobic nano silicon dioxide, 5 parts of foaming agent cyclopentane, 5 parts of polysiloxane and 5 parts of alkane block copolymer, 1.5 parts of antioxidant, 2.0 parts of light stabilizer, 10 parts of diethylene glycol, 8 parts of glycerol and trimethylolpropane, 1 part of catalyst T12 and 10 parts of black paste into a container;
stirring the container at a high speed for 2min under a stirring machine of 2000 rpm to ensure uniform mixing to obtain a component A;
the preparation of the component B comprises the following steps:
keeping the MDI at 60 ℃ for 2 hours to obtain a standby material; adding 600 parts of dehydrated castor oil into a reaction kettle, starting stirring and simultaneously heating to 40 ℃; adding 800 parts of standby materials into a stirring reaction kettle, heating to 50 ℃, and keeping for 30min; heating the temperature of the reaction kettle to 60 ℃ and preserving the temperature for 1h;
heating the temperature of the reaction kettle to 70 ℃ and preserving the temperature for 1h; heating the temperature of the reaction kettle to 80 ℃ and preserving the temperature for 2 hours; cooling the temperature of the reaction kettle to 60 ℃, adding 78 parts of 2-methyl-1, 3-propylene glycol, and preserving the temperature for 1 hour;
heating to 70 ℃, and keeping the temperature for 1h; heating to 80 ℃, and reacting for 2 hours in a heat preservation way; cooling to 40 ℃ and discharging to obtain the-NCO component prepolymer B component.
Preparing a foaming material:
and (3) putting the component A and the component B into a container according to the weight part ratio of 5, stirring at a high speed for 15s under a stirring machine of 2500 revolutions per minute, coating on a coating machine, and curing the coated sample in an oven at 80 ℃ for 4 hours to obtain the foaming material.
In the present invention:
the hydrolysis of ester group in the polyurethane system can generate carboxylic acid, the carboxylic acid can further accelerate the hydrolysis, the hydrolysis-resistant stabilizer added in the component A can have a vigorous reaction with the carboxylic acid generated by the hydrolysis of polyurethane, so that the content of the carboxylic acid in the system is reduced, the further occurrence of the hydrolysis is inhibited, and the performance reduction of the polyurethane molecular chain caused by hydrolytic cleavage is reduced.
The castor oil is a plant-based polyol with a certain hydrophobic characteristic, has stronger hydrolysis resistance compared with common polyether polyol, and further improves the hydrolysis resistance of the castor oil through the modification of the PTEMG and isocyanate.
Although castor oil has strong hydrolysis resistance, the molecules of castor oil contain a small amount of ester groups, so the ester groups are hydrolyzed to form carboxylic acid, and the carboxylic acid generated by hydrolysis can be timely and clearly removed by adding a small amount of hydrolysis resistant agent in the formula, thereby inhibiting further hydrolysis.
A small amount of nano hydrophobic silicon dioxide is added into the system, so that the hydrophobic capacity of the foam can be further improved, namely the contact area of the molecular chain of the water molecule polyurethane is reduced, and the hydrolysis rate can be reduced to a certain extent.
The hydrolysis of the component B is further reduced by pre-polymerization of 2 methyl-1, 3-propanediol, castor oil and isocyanate, wherein the 2 methyl-1, 3-propanediol can improve the hydrophobicity to a certain extent due to the-CH 3 containing a branched chain, which is helpful for reducing the hydrolysis.
Comparative example 1:
samples were prepared according to the procedure of the examples except that in the comparative example one, no hydrolysis resistance stabilizer was added, and then the samples were tested for density, compressive stress, and compression set in a double 85 environment.
Comparative example 2:
samples were prepared according to the procedure of example except that the nano hydrophobic silica was not added in comparative example two, and then the samples were tested for density, compressive stress, and compression set under a double 85 environment.
Comparative example 3:
samples were prepared according to the procedure of the example except that in comparative example three, no hydrolysis resistance stabilizer was added, no nano hydrophobic silica was added, and then the samples were tested for density, compressive stress, and compression set in a dual 85 environment.
The test method of the invention is based on the following steps:
(1) The high-temperature and high-humidity environment is an environment with the temperature of 85 ℃ and the humidity of 85 percent;
(2) The compressive stress Test reference standard is ASTM 3547Test C;
(3) The compression set test reference standard is GB/T6669-2008;
(4) The compressive stress decay Test procedure comprises compressing the sample according to GB/T6669-2008 at 85 deg.C and 85% RH for 22h and 168h, taking out the sample after a specified time and recovering for 30min, and performing compressive stress Test according to ASTM 3547Test C, and calculating the difference delta F/F0 of the compressive stress of the two tests.
The results of the physical property test of the polyurethane foam are shown in Table 1
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The high-temperature and high-humidity resistant polyurethane foam material is characterized by comprising the following steps of:
the component A is prepared by the following steps:
s1: the method comprises the steps of selecting castor oil polyol with a hydrophobic structure as a base, and carrying out prepolymerization on one or more of MDI, TDI or IPDI, PTEMG and castor oil to obtain a hydroxyl component polymer polyol component I;
s2: placing 60-75 parts of the first component obtained in the step S1 into a container;
s3: adding 0.5-5.0 parts of hydrolysis resistant agent, 1.0-5.0 parts of hydrophobic nano silicon dioxide, 0.5-5 parts of foaming agent, 1.5-10 parts of silicone oil, 0.1-1.5 parts of antioxidant, 0.2-2.0 parts of light stabilizer, 2-10 parts of chain extender, 2-8 parts of cross-linking agent, 0.1-1 part of catalyst and 3-10 parts of black paste into a container;
s4: stirring the container at a high speed for 2min under a stirring machine of 2000 rpm to ensure uniform mixing to obtain a component A;
the preparation of the component B comprises the following steps:
s5: one or more of MDI, TDI or IPDI is subjected to heat preservation for 2 hours at the temperature of 60 ℃ to obtain a standby material;
s6: adding 400-600 parts of dehydrated castor oil into a reaction kettle, starting stirring and simultaneously heating to 40 ℃;
s7: adding 600-800 parts of the standby material in the step S5 into a stirring reaction kettle, heating to 50 ℃ and keeping for 30min;
s8: heating the temperature of the reaction kettle to 60 ℃ and preserving the temperature for 1h;
s9: heating the temperature of the reaction kettle to 70 ℃ and preserving the temperature for 1h;
s10: heating the temperature of the reaction kettle to 80 ℃ and preserving the temperature for 2 hours;
s11: cooling the temperature of the reaction kettle to 60 ℃, adding 78 parts of 2-methyl-1, 3-propylene glycol, and preserving the temperature for 1 hour;
s12: heating to 70 ℃, and preserving the heat for 1h;
s13: heating to 80 ℃, and reacting for 2 hours in a heat preservation way;
s14: cooling to 40 ℃ and discharging to obtain a-NCO component prepolymer B component;
preparing a foaming material:
and (3) putting the component A and the component B into a container according to the weight part ratio of 3-5, stirring at a high speed for 15s under a stirrer of 2500 revolutions per minute, coating on a coating machine, and curing the coated sample in an oven at 80 ℃ for 4 hours to obtain the foaming material.
2. The high temperature and high humidity resistant polyurethane foam material according to claim 1, wherein the specific steps of the component A are as follows:
s11: one or more of MDI, TDI or IPDI is subjected to heat preservation for 2 hours at 60 ℃ to obtain a standby material;
s12: adding 60-80 parts of dehydrated castor oil and 20-40 parts of PTEMG into a reaction kettle, starting stirring and simultaneously heating to 40 ℃;
s13: adding 2-10 parts of the standby material prepared in the step S11 into a stirring reaction kettle, heating to 50 ℃ and keeping for 30min;
s14: heating the temperature of the reaction kettle to 60 ℃ and preserving the temperature for 1h;
s15: heating the temperature of the reaction kettle to 70 ℃ and preserving the temperature for 1h;
s16: and (3) heating the reaction kettle to 80 ℃, preserving the temperature for 3h, naturally cooling to 40 ℃, and discharging to obtain the hydroxyl component polymer polyol component I.
3. The foaming material of claim 1, wherein the hydrolysis resistant agent is a carbodiimide-modified polymer.
4. The foaming material of claim 1, wherein the blowing agent is one or more of water, HCFC-141B and cyclopentane.
5. The high temperature and high humidity resistant polyurethane foam material as claimed in claim 1, wherein the silicone oil is 1-5 parts of silicone oil I, 0.5-5 parts of silicone oil II, both the silicone oil I and the silicone oil II are hydrolysis resistant silicone oil, the silicone oil I is polysiloxane, and the silicone oil II is alkane block copolymer.
6. The high temperature and high humidity resistant polyurethane foam material as claimed in claim 1, wherein the chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, and diethylene glycol.
7. The foaming material of claim 1, wherein the cross-linking agent is one or more of glycerol, trimethylolpropane, polyether 310 with molecular weight of 100 and functionality of 3.
8. The foaming material of claim 1, wherein the catalyst is one or more of A33, T9 and T12.
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Denomination of invention: A high-temperature and high humidity resistant polyurethane foam material Effective date of registration: 20230414 Granted publication date: 20221206 Pledgee: Agricultural Bank of China Limited by Share Ltd. South Lake branch Pledgor: ZHEJIANG QINGYOU MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980038087 |