CN112225869B - Polyurethane microporous foam with uniform pore diameter and preparation method thereof - Google Patents
Polyurethane microporous foam with uniform pore diameter and preparation method thereof Download PDFInfo
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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Abstract
The invention discloses a uniform-aperture polyurethane microporous foam, which comprises a component A, a component B, a component C and a component D, wherein the component A is an isocyanate mixture or a modified isocyanate mixture; the component B comprises water and a catalyst B; the component C is isocyanate prepolymer; the component D comprises polyether polyol, a chain extender, a catalyst D and a surface tension regulator. The invention firstly reacts isocyanate and water to a certain degree under the action of the catalyst, realizes that supersaturation exists in the system and tiny bubbles are separated out, simultaneously, the reaction is not complete, carbon dioxide can be continuously generated, and then a product of the preliminary reaction is added into a mixed component which does not generate chemical reaction gas, so as to introduce a core point, carry out the growth of foam pores on the introduced core point, and finally, the polyurethane microporous foam with uniformly distributed pore diameters is formed by curing and forming.
Description
Technical Field
The invention belongs to the field of foaming materials, and particularly relates to polyurethane microporous foam with uniform pore diameter and a preparation method thereof.
Background
The polyurethane foaming material is common and has wide application field. Polyurethane microporous foam in the form of a film is widely used in the fields of handheld electronic devices, household electronic devices, business electronic devices, and the like because of its special sealing properties and shock absorbing properties.
Polyurethane foaming materials are generally one-component or two-component polyurethane products, wherein one-component means that various raw materials required for foaming are directly mixed in a container at one time, and then poured or coated on a substrate, and the mixture is cured to obtain the required product. The bi-component is prepared by dividing raw materials into two components, and storing separately, wherein one component is hydroxyl component, and is mixture or poly-polybasic alcohol of polyalcohol, catalyst, chain extender and waterA mixture of alcohol, a prepolymer of a chain extender, water, and a catalyst; the other component is an isocyanate component, i.e. an isocyanate or isocyanate modification, prepolymer. Wherein water is used as gas source in the foaming process and can react with isocyanate to release CO2。
In summary, the existing systems release CO by reaction of water with isocyanate2Growth of bubbles is carried out, but this problem is seen in two ways: (1) if the raw material is strictly vacuumized, the fact that only gas generated by reaction in the system is meant means that the bubble growth nucleation points are lost, and finally, the solidified foaming body does not have bubbles and is of a solid structure; (2) if the raw material has air or other gas stirred in, the gas-liquid mixing mode introduces a nucleation point, and CO released by the reaction can be discharged2The growth of bubbles is carried out, but the difficulty of gas-liquid mixing is that the stable existence and the uniform distribution of gas in liquid have extremely strict requirements on liquid substances, and the conventional raw materials can hardly realize the growth.
However, it is found that, although carbon dioxide generated by chemical reaction is the only source of gas in the polyurethane foaming and curing system, the growth nucleation sites in the initial stage of bubble growth are not carbon dioxide generated by reaction, but are gas which is not uniformly distributed and stirred into the raw material system, and in the process of foam growth, new bubbles are not generated, but a large amount of bubbles disappear. If there is no nucleation site for the growth of reaction gas, even if the chemical reaction releases more carbon dioxide, there is only a merging and defoaming process, and there is no cell growth and formation (see Saunders, J.H. and Frisch, k.c. polyurethane: chemistry and technology, v.I and II. applied science purifier, london 1962. and Bessette, M.D. andstrongstrom, D.W. Rheology of model polyurethane foam.Polymer.Process.eng., 1985(3): 25-35.).
The air mixed and stirred in has the problems of incapability of quantification, uneven mixing and uneven distribution, so that the air is difficult to be used as a nucleation point, and the foam with excellent pore size distribution is finally obtained, and the excellent compression resistance of the foam is closely related to the uniform pore distribution.
Some products can be added with a certain amount of low-boiling-point micromolecule liquid substances, and the liquid substances volatilize after the temperature is higher than the boiling point of the liquid substances in the process of curing reaction of the two components, and gas generated in the volatilization process is used as a gas source. However, the volatilization of such small molecular liquid substances as monochloro-methane, dichloromethane and cyclohexane can cause serious ecological problems, namely ozone layer destruction or atmospheric environment and workshop environment pollution.
Therefore, how to solve the distribution and introduction of nucleation sites before the growth of bubbles to prepare a foam material with uniform pore size and how to avoid the environmental pollution problem caused by the production process becomes a problem to be treated urgently.
Disclosure of Invention
In view of the above drawbacks or needs for improvement in the prior art, the present invention provides a uniform pore size polyurethane microporous foam and a method for preparing the same, wherein the prepared foam has good pore size distribution and excellent compression resistance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a uniform pore size polyurethane microcellular foam characterized by comprising component a, component B, component C and component D, wherein,
the component A is an isocyanate mixture or a modified isocyanate mixture;
the component B comprises water and a catalyst B;
the component C is isocyanate prepolymer;
the component D comprises polyether polyol, a chain extender, a catalyst D and a surface tension regulator.
The reaction of isocyanate, polyol and chain extender is the gel reaction of the system, the reaction of isocyanate and water is the gas-forming reaction of the system, and the isocyanate, the polyol and the chain extender are combined with each other to finally form the foaming body with a certain hole type structure.
The invention firstly utilizes the reaction of isocyanate and water to generate gas, namely CO in liquid phase2The generated gas gradually escapes to form bubbles after reaching the supersaturated concentration in the liquid phase; at the same time, after the mixture of isocyanate and water is reacted, it is not gas-liquid mixedBefore the compound (or only a part of gas-liquid mixture), the compound is mixed with a mixture of isocyanate, polyol and a chain extender, the process is similar to a liquid-liquid mixing process, and similar molecular structures exist between A + B and C + D, so that the uniformity and consistency can be ensured after mixing. The gas generated in A + B and precipitated due to supersaturation is actually introduced into the mixture of ABCD, becomes a uniformly distributed nucleation point, namely a growth point for generating reaction gas subsequently, and finally can become bubbles (cells) of a solidified foaming body, and the uniform nucleation point determines the uniform consistency of the pore size of the finally prepared foam.
The catalysts B and D are catalysts, and are used for distinguishing the catalysts in the component B from the catalysts in the component D.
Preferably, the ratio of the amount of the functional groups of the component A to the reactive groups of the component B is 1:1 to 1.05:1, the mass ratio of the functional group of the component C to the functional group of the component D is 1: 1-1.05: 1. theoretically, in the polyurethane raw material, if the mass ratio of the functional group-NCO of the component A to the reactive group-OH in the component B is 1:1, the molecular weight of the final product can be infinitely large, and in the actual production process, the side reaction in the system is eliminated by increasing the ratio of-NCO due to the side reaction, so that the final reaction is not influenced.
Preferably, the ratio of the mixture AB of component A and component B to the mixture CD of component C and component D is from 20% to 40% by weight. The amount of isocyanate and water reacted to generate gas determines the density of the product, and indirectly influences the hardness. Meanwhile, polyurea and biuret can be generated, and the modulus is higher; meanwhile, in the polyurethane system, isocyanate and a chain extender are used as hard segments, and polyol is used as soft segments to form a special soft-segment and soft-segment microphase separation structure, and the hard segments determine the performances of rigidity, modulus, hardness and the like of the product, so that the proportion range of the mixture AB in the mixture CD is designed to be 20-40 wt%, the support property and the bearing property of the product are ensured, and the final foam product is endowed with good weather resistance and compression resistance; but also ensures the reasonable modulus and moderate hardness of the product, and meets the use requirement of the final electronic product foam.
Preferably, in component A, the viscosity of the isocyanate mixture or modified isocyanate mixture is from 20mPa.s/25 ℃ to 300mPa.s/25 ℃;
in the component B, water is deionized water, and the catalyst B is an amine catalyst;
in the component C, the isocyanate prepolymer is a prepolymer product of excessive isocyanate and polyether polyol or polyester polyol, and the viscosity is 3000 mPa.s/25-5000 mPa.s/25 ℃;
the viscosity of the component D is 600 mPa.s/25-1000 mPa.s/25 ℃, wherein the polyether polyol is ethylene (propylene) oxide polyether polyol, the chain extender is micromolecular dihydric alcohol, the catalyst D is an organic metal catalyst, and the surface tension regulator is liquid organic silicone oil. Regarding the selected viscosity, the component B is a mixture of water and a catalyst, the viscosity is extremely low, and the component A is a raw material with lower viscosity in order to ensure the uniform mixing of the AB mixture. The component C is a prepolymer which is a product obtained by reacting isocyanate with a polymeric polyol, has a larger molecular weight and a higher viscosity than a monomer or a macromolecule, but the initial viscosity of the mixture of the component C and the component D is not large, preferably 2000-4000, so that the component D selects polyether polyol with lower viscosity, but does not select polyester polyol with high viscosity. Meanwhile, the mixture CD has proper viscosity, which is beneficial to the distribution of the mixture AB introduced into the nucleation sites, the diffusion and combination of gases generated by the reaction, and the uniformity of the gel and gas reaction, and the final curing rate and the microscopic aperture ratio meet the requirements.
Preferably, in component a:
the isocyanate mixture is a mixture of more than two of toluene diisocyanate, isophorone diisocyanate and liquefied diphenylmethane diisocyanate;
the modified isocyanate mixture is a mixture of two or more of toluene diisocyanate, isophorone diisocyanate and liquefied diphenylmethane diisocyanate;
in the component B, the catalyst B is one or two of triethyldiamine, triethylamine or dimethylethanolamine;
in the component C, the isocyanate prepolymer is a prepolymer of excessive isocyanate and polyether polyol or polyester polyol, wherein the isocyanate is one or two of toluene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate, the polyester polyol is one or more of polyethylene glycol adipate diol, poly (1, 4-butylene glycol adipate) diol and poly (1, 3-propylene glycol adipate diol), and the polyether polyol is one or more of polyethylene oxide (propylene) diol using ethylene glycol as an initiator, polyethylene oxide (propylene) triol using glycerol as an initiator, polyethylene oxide-propylene copolymer diol using ethylene glycol as an initiator and polyethylene oxide-propylene copolymer triol using glycerol as an initiator;
in the component D, the polyether polyol is one or more of polyoxyethylene (propylene) glycol taking ethylene glycol as an initiator, polyoxyethylene (propylene) triol taking glycerol as an initiator, polyoxyethylene-propylene copolymer glycol taking ethylene glycol as an initiator and polyoxyethylene-propylene copolymer triol taking glycerol as an initiator; the chain extender is one or two of ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol, and the catalyst d is one or two of bismuth octoate and bismuth isooctanoate; the surface tension regulator is polydimethylsiloxane.
Preferably, the molecular weight of the polyether polyol is 800-6000, and the molecular weight of the polyester polyol is 800-6000. The molecular weight of the conventional polymeric polyol is 600-7000, and the molecular weight range of the existing raw materials is substantially covered by the selection of 800-6000 in the present invention.
Preferably, in the component B, the ratio of the catalyst B to water is 0.03 to 0.07 percent by weight;
in the component C, the content of isocyanate groups in the isocyanate prepolymer is 15-20 wt%;
in the component D, the ratio of the addition amount of the chain extender to the polyether polyol is 1-3 wt%, the ratio of the addition amount of the catalyst D to the polyether polyol is 0.04-0.08 wt%, and the ratio of the addition amount of the surface tension regulator to the polyether polyol is 0.5-1.5 wt%.
The isocyanate content of the isocyanate prepolymer is selected to be 15-20 wt%, so that reasonable viscosity is ensured, and smooth completion of curing forming and pore forming is ensured; the chain extender is selected from 1wt% -3wt%, the mixture AB accounts for 20wt% -40wt% of the mixture CD, and the proportion of the hard segment in the total system is reasonable, so that the final product has good physical properties and hardness. The addition amount of the catalyst is an auxiliary of a chemical reaction, is more critical, and is strictly matched with the stirring speed, the stirring time and the standing time, when the addition amount is too much, the reaction speed of gel and gas generation is not balanced, and the prepared foam can have the problems of shrinkage, collapse and the like, so that the addition amount of the catalyst b is selected to be 0.03-0.07 wt% (weight ratio to water), and the addition amount of the catalyst D is selected to be 0.04-0.08 wt% (weight ratio to polyhydric alcohol in the component D).
According to another aspect of the invention, the invention also provides a preparation method of the polyurethane microporous foam with uniform pore size, which is characterized in that,
the method comprises the following steps:
1) uniformly mixing the component A and the component B to form a mixture AB, and uniformly mixing the component C and the component D to form a mixture CD; wherein the mass ratio of the functional group of the component A to the reactive group of the component B is 1: 1-1.05: 1, the mass ratio of the functional group of the component C to the functional group of the component D is 1: 1-1.05: 1;
2) after the mixture AB stands still, adding the mixture AB into the mixture CD and uniformly mixing to form a mixture ABCD; wherein the ratio of the mixture AB to the mixture CD is 20wt% -40 wt%;
3) coating the mixture ABCD obtained in the step 2) on a PET film, and heating and curing to obtain the polyurethane microporous foam with uniform pore size.
Preferably, in step 1), the rotation speed of mixing the component A with the component B is 6000rpm-1000rpm, the mixing time is 3s-5s, the rotation speed of mixing the component C with the component D is 6000rpm-10000rpm, and the mixing time is 5s-8 s.
The standing time of the mixture AB in the step 2) is 5s-8s, and the standing time of the mixture CD is 4s-6 s;
the mixing time of the mixture AB and the mixture CD is 5s-8s, and the rotating speed is 8000rpm-10000 rpm.
Preferably, the coating thickness in step 3) is 0.1mm to 0.5 mm; the heating curing temperature is 115-120 ℃; the heating curing time is 15 min-20 min. In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
the invention mixes the component A and the component B, and the isocyanate mixture or the modified isocyanate mixture reacts with water to a certain degree under the action of the catalyst, so that the tiny carbon dioxide bubbles (the component A and the component B generate gas through liquid-liquid mixing reaction, the mixture AB is low-viscosity liquid, and the generated carbon dioxide gas can reach supersaturation and finally escape due to the gradual increase of the concentration after the reaction) which are separated out due to supersaturation in the system are realized, simultaneously, isocyanate and water are not completely reacted, so that carbon dioxide can be continuously generated, then a product obtained by the primary reaction of the component A and the component B is added into a mixture CD which does not generate chemical reaction gas, thereby leading in carbon dioxide gas as a core point, growing foam holes on the introduced core point, and finally curing and forming to obtain the polyurethane microporous foam with uniformly distributed pore diameters.
The foam material is different from the conventional one-step method and two-step method preparation methods, but creatively adopts 4 components, and adopts a mode of reaction-recombination, so that the problem of the introduction of nucleation core points is solved, and the problem of the dispersion of the core points in a system is solved by utilizing the advantage of higher compatibility of the same system; thirdly, after the nuclear points are introduced and uniformly distributed, the carbon dioxide generated by the reaction of the system per se can be used for growing bubbles by relying on the nuclear points; finally, the foam is successfully fixed by means of the viscosity change of the system and the adjustment of the surface tension regulator, and the polyurethane microporous foam cotton with uniform foam holes is formed.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The component A adopts toluene diisocyanate and isophorone diisocyanate with the mass ratio of 1:1, 36.35g of each component, and the viscosity is controlled to be 30 mPa.s.
The component B adopts 6.63g of water and 0.0027g of triethyldiamine;
the ratio of the amount of species of functional groups of component A to the reactable reactive groups of component B is 1.01:1.
And the component C is prepared by adopting 20.07g of toluene diisocyanate, 20.07g of diphenylmethane diisocyanate, 12.54g of polyethylene glycol adipate diol with the molecular weight of 800, 12.54g of poly-1, 4-butanediol adipate diol with the molecular weight of 1000 and 16.72g of poly-1, 3-propylene glycol adipate diol with the molecular weight of 1500 to carry out prepolymerization to form an isocyanate prepolymer, wherein the mass fraction of isocyanate groups in the isocyanate prepolymer is 16 wt%, and the viscosity is controlled to be 3500mPa.
Component D, using 25g of polyoxyethylene glycol with molecular weight of 800, 62.5g of polyoxypropylene glycol with molecular weight of 1000, 37.5g of polyoxyethylene-propylene oxide co-triol with molecular weight of 6000, 1.25g of ethylene glycol, 0.0625g of bismuth isooctanoate and 1.25g of polydimethylsiloxane, and mixing the components to obtain the viscosity of 700 mPa.s.
The ratio of the amount of species of functional groups of component C to component D was 1.01:1.
The preparation method comprises the following steps:
(a) mixing component A with component B at 6000rpm for 5 s; mixing component C with component D at 6000rpm for 5 s;
(b) standing a mixture AB formed by the component A and the component B for 5s, standing a mixture CD formed by the component C and the component D for 5s, then adding the mixture AB formed by the component A and the component B into the mixture CD formed by the component C and the component D, and stirring at 10000rpm for 5 s;
(c) the 4-component mixture described above was coated on a PET substrate at a coating thickness of 0.2mm and transferred to a 115 ℃ oven for 15 minutes.
Example 2
The component A adopts toluene diisocyanate and liquefied diphenylmethane diisocyanate with the mass ratio of 1:1, each 25.42g, and the viscosity is controlled to be 80 mPa.s.
The component B adopts 3.5g of water, 0.00105g of triethyldiamine and 0.0007g of triethylamine;
the ratio of the amount of species of functional groups of component a to the reactable reactive groups of component B is 1.03: 1.
And the component C is prepared by adopting 12.82g of toluene diisocyanate, 12.82g of isophorone diisocyanate, 5.45g of polyethylene glycol adipate diol with the molecular weight of 6000, 5.45g of polyoxyethylene triol with the molecular weight of 800, 8.17g of polyoxypropylene diol with the molecular weight of 3000 and 8.17g of polyoxypropylene triol with the molecular weight of 2000 to carry out prepolymerization to form an isocyanate prepolymer, wherein the mass fraction of isocyanate groups in the isocyanate prepolymer is 18 wt%, and the viscosity is controlled to be 4000mPa.
Component D was prepared from 10g of a polyethylene oxide-propylene copolymer diol having a molecular weight of 2000, 30g of a polyethylene oxide-propylene copolymer triol having a molecular weight of 3000, 40g of a polyethylene oxide diol having a molecular weight of 800, 20g of a polypropylene oxide diol having a molecular weight of 1500, 2g of 1, 3-propanediol, 0.02g of bismuth isooctanoate, 0.04g of bismuth neodecanoate, and 0.8g of polydimethylsiloxane, and the mixture was mixed to give a viscosity of 800 mPa.s.
The ratio of the amount of species of functional groups of component C to component D was 1.03: 1.
The preparation method comprises the following steps:
(a) mixing component A and component B for 3s at a mixing speed of 10000 rpm; mixing component C with component D at 10000rpm for 6 s;
(b) standing the mixture of the component A and the component B for 8s, standing the mixture of the component C and the component D for 6s, then adding the mixture AB formed by the component A and the component B into the mixture CD formed by the component C and the component D, and stirring at 8000rpm for 8 s;
(c) the 4-component mixture was coated onto a PET substrate at a coating thickness of 0.3mm and transferred to a 120 ℃ oven for 18 minutes.
Example 3
The component A adopts 11.90g of toluene diisocyanate, 11.90g of isophorone diisocyanate and 11.90g of liquefied diphenylmethane diisocyanate in the mass ratio of 1:1:1, and the viscosity is controlled to be 150 mPa.s.
The component B adopts 2.62g of water and 0.00157g of dimethylethanolamine;
the ratio of the amount of species of functional groups of component a to the reactable reactive groups of component B is 1.04: 1.
And the component C is prepared by carrying out prepolymerization on 15.73g of diphenylmethane diisocyanate, 0.84g of poly-1, 3-propylene glycol adipate diol with the molecular weight of 1000, 0.84g of poly-1, 4-butylene glycol adipate diol with the molecular weight of 2000, 3.34g of polyoxyethylene-propylene copolymer triol with the molecular weight of 800 and 3.34g of polyoxyethylene-propylene copolymer triol with the molecular weight of 6000 to form an isocyanate prepolymer, wherein the mass fraction of isocyanate groups in the isocyanate prepolymer is 19 wt%, and the viscosity is controlled to be 4500 mPa.s.
Component D, using 20g of polyoxypropylene diol 3500 molecular weight, 40g of polyoxyethylene diol 2000 molecular weight, 40g of polyoxyethylene-propylene copolymer triol 5000 molecular weight, 1.5g of 1, 4-butanediol, 0.07g of bismuth isooctanoate and 1.2g of polydimethylsiloxane, and mixing them to obtain a viscosity of 900 mPa.s.
The ratio of the amount of species of functional groups of component C to component D was 1.04: 1.
The preparation method comprises the following steps:
(a) mixing component A with component B at 7000rpm for 4 s; mixing component C with component D at 8000rpm for 8 s;
(b) standing the mixture of the component A and the component B for 6s, standing the mixture of the component C and the component D for 5s, then adding the mixture AB formed by the component A and the component B into the mixture CD formed by the component C and the component D, and stirring at 9000rpm for 6 s;
(c) the 4-component mixture described above was coated on a PET substrate at a coating thickness of 0.4mm and transferred to a 118 ℃ oven for 20 minutes.
Example 4
The component A adopts 40.12g of isophorone diisocyanate and liquefied diphenylmethane diisocyanate in a mass ratio of 1:1, and the viscosity is controlled to be 20 mPa.s.
Component B was 5.83g of water, 0.00175g of triethyldiamine;
the ratio of the amount of substance of the functional groups of component A to the reactable reactive groups of component B is 1:1.
And the component C is prepared by adopting 29.89g of diphenylmethane diisocyanate, 29.89g of isophorone diisocyanate and 52.83g of polyethylene glycol adipate glycol with the molecular weight of 1000 to carry out prepolymerization to form an isocyanate prepolymer, wherein the mass fraction of isocyanate groups in the isocyanate prepolymer is 15wt%, and the viscosity is controlled to be 3000 mPa.s.
Component D, 100g of polyoxyethylene-propylene copolymer triol with molecular weight of 800, 0.5g of 1, 4-butanediol, 0.5g of ethylene glycol, 0.04g of bismuth isooctanoate and 1.5g of polydimethylsiloxane, and the viscosity after mixing is 600 mPa.s.
The ratio of the amount of species of functional groups of component C to component D is 1:1.
The preparation method comprises the following steps:
the above mixture of 4 components was coated to a thickness of 0.1mm, and the rest of this example was substantially the same as example 1, and thus detailed description thereof is omitted.
Example 5
The component A adopts isophorone diisocyanate and liquefied diphenylmethane diisocyanate with the mass ratio of 1:1, each 12.41g, and the viscosity is controlled at 300 mPa.s.
Component B was 1.21g of water, 0.00085g of triethyldiamine;
the ratio of the amount of species of functional groups of component a to the reactable reactive groups of component B is 1.05: 1.
And the component C is prepared by adopting 6.46g of toluene diisocyanate, 6.46g of isophorone diisocyanate, 6.83g of 6000 molecular weight 1, 4-butanediol adipate diol and 6.83g of 6000 molecular weight polyethylene oxide-propylene copolymer triol to carry out prepolymerization to form an isocyanate prepolymer, wherein the mass fraction of isocyanate groups in the isocyanate prepolymer is 20wt%, and the viscosity is controlled to be 5000mPa.
And the component D comprises 50g of polyoxyethylene-propylene copolymer triol with the molecular weight of 6000, 50g of polyoxypropylene diol with the molecular weight of 6000, 3.0g of 1, 3-propylene glycol, 0.08g of bismuth neodecanoate and 0.5g of polydimethylsiloxane, and the viscosity of the mixture is 1000mPa.s after the mixture is mixed.
The ratio of the amount of species of functional groups of component C to component D was 1.05: 1.
The preparation method comprises the following steps:
the above mixture of 4 components was coated to a thickness of 0.5mm, and the rest of this example was substantially the same as example 1, and thus detailed description thereof is omitted.
Comparative example 1:
all the materials in example 4 were mixed and the polyurethane foam was prepared directly by one-step process.
Comparative example 2:
polyurethane foam was prepared by mixing component A and component C, component B and component D, and a mixture AC of component A and component C as an-NCO component and a mixture BD of component B and component D as an-OH component in example 5, and then mixing mixture AC and mixture BD twice.
Comparative example 3:
the component A adopts liquefied diphenylmethane diisocyanate, the mass ratio of the liquefied diphenylmethane diisocyanate is 1:1, 14.52g of each component, and the viscosity is controlled to be 800 mPa.s.
The component B adopts 0.052g of water and 0.00001g of triethylamine, and the active group ratio of the component A to the component B is 1.01:1.
And the component C adopts diphenylmethane diisocyanate, 68.79g and 22.85g of 10000 molecular weight polyethylene glycol adipate diol to carry out prepolymerization, the mass fraction of isocyanate groups is 25 wt%, and the viscosity is controlled to be 7000mPa.
Component D, 100g of molecular weight polyethylene oxide-propylene copolymer triol, 1.0g of ethylenediamine, 0.08g of bismuth isooctanoate and 1.2g of polydimethylsiloxane, and the viscosity of the mixture is 400 mPa.s. Wherein the ratio of C to D functional groups is 1.05: 1.
This comparative example was prepared in the same manner as example 5.
The performance test indexes of examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 foam property testing table
As can be seen from Table 1, in the case of changing the combination of the types of the isocyanate and the polyol and the formulation ratio, the final pore diameter difference of the polyurethane foam does not exceed 65 microns along with the change of the ratio of the mixture AB to the mixture CD (20 wt% -40 wt%), and the minimum pore diameter difference is only 35 microns, so that the uniformity of the pore diameter is good; meanwhile, the maximum pore size of all the examples is only 170 micrometers, the minimum pore size is 65 micrometers, and the distribution of the overall pore size is in the category of micropores.
In addition, in examples 1-5, the prepared foam has good pore size distribution and excellent compression resistance, while in the comparative example, the conventional one-step method, two-step method or the difference of the material components with the examples is not beneficial to the growth and formation of the cells, and the foam with good pore size distribution is difficult to obtain, and the excellent compression resistance of the foam is closely related to the uniform cell distribution, thereby further influencing the compression resistance of the foam.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. The polyurethane microporous foam with uniform pore diameter is characterized by comprising a component A, a component B, a component C and a component D, wherein,
the component A is an isocyanate mixture or a modified isocyanate mixture;
the component B comprises water and a catalyst B, wherein the water is deionized water, and the catalyst B is an amine catalyst;
the component C is isocyanate prepolymer which is a prepolymer product of excessive isocyanate and polyether polyol or polyester polyol;
the component D comprises polyether polyol, a chain extender, a catalyst D and a surface tension regulator, wherein the polyether polyol is ethylene oxide polyether polyol or propylene oxide polyether polyol, the chain extender is micromolecular dihydric alcohol, the catalyst D is an organic metal catalyst, and the surface tension regulator is liquid organic silicone oil;
the molecular weight of the polyether polyol is 800-6000, and the molecular weight of the polyester polyol is 800-6000;
the preparation method of the polyurethane microporous foam with uniform pore diameter comprises the following steps:
1) uniformly mixing the component A and the component B to form a mixture AB, and uniformly mixing the component C and the component D to form a mixture CD; wherein the mass ratio of the functional group of the component A to the reactive group of the component B is 1: 1-1.05: 1, the mass ratio of the functional group of the component C to the functional group of the component D is 1: 1-1.05: 1;
2) after the mixture AB stands still, adding the mixture AB into the mixture CD and uniformly mixing to form a mixture ABCD; wherein the ratio of the mixture AB to the mixture CD is 20wt% -40 wt%;
3) coating the mixture ABCD obtained in the step 2) on a PET film, and heating and curing to obtain the polyurethane microporous foam with uniform pore size;
in the step 1), the rotating speed of the component A and the component B is 6000rpm-10000rpm when being mixed, the mixing time is 3s-5s, the rotating speed of the component C and the component D is 6000rpm-10000rpm when being mixed, and the mixing time is 5s-8 s;
the standing time of the mixture AB in the step 2) is 5s-8s, and the standing time of the mixture CD is 4s-6 s;
the mixing time of the mixture AB and the mixture CD is 5s-8s, and the rotating speed is 8000rpm-10000 rpm.
2. The polyurethane microcellular foam with uniform pore size according to claim 1,
in the component A, the viscosity of the isocyanate mixture or the modified isocyanate mixture is 20 mPa.s/25-300 mPa.s/25 ℃; in the component C, the viscosity of the isocyanate prepolymer is 3000 mPa.s/25-5000 mPa.s/25 ℃;
the viscosity of the component D is 600 mPa.s/25-1000 mPa.s/25 ℃.
3. The microcellular polyurethane foam with uniform pore size as claimed in claim 1, wherein in component a, the isocyanate or the modified isocyanate mixture is a mixture of two or more of toluene diisocyanate, isophorone diisocyanate and liquefied diphenylmethane diisocyanate;
in the component B, the catalyst B is one or two of triethyldiamine, triethylamine or dimethylethanolamine;
in the component C, the isocyanate prepolymer is a prepolymer of excessive isocyanate and polyether polyol or polyester polyol, wherein the isocyanate is one or two of toluene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate, the polyester polyol is one or more of polyethylene glycol adipate diol, poly (1, 4-butylene glycol adipate) diol and poly (1, 3-propylene glycol adipate diol), and the polyether polyol is one or more of polyethylene oxide diol or polypropylene oxide diol using ethylene glycol as an initiator, polyethylene oxide triol or polypropylene oxide triol using glycerol as an initiator, polyethylene oxide-propylene copolymer diol using ethylene glycol as an initiator and polyethylene oxide-propylene copolymer triol using glycerol as an initiator;
in the component D, the polyether polyol is one or more of polyoxyethylene glycol or polyoxypropylene glycol taking ethylene glycol as an initiator, polyoxyethylene triol or polyoxypropylene triol taking glycerol as an initiator, polyoxyethylene-propylene copolymer glycol taking ethylene glycol as an initiator and polyoxyethylene-propylene copolymer triol taking glycerol as an initiator; the chain extender is one or two of ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol, and the catalyst d is one or two of bismuth octoate and bismuth isooctanoate; the surface tension regulator is polydimethylsiloxane.
4. The polyurethane microcellular foam with uniform pore size according to claim 1,
in the component B, the ratio of the catalyst B to water is 0.03-0.07 wt%;
in the component C, the content of isocyanate groups in the isocyanate prepolymer is 15-20 wt%;
in the component D, the ratio of the addition amount of the chain extender to the polyether polyol is 1-3 wt%, the ratio of the addition amount of the catalyst D to the polyether polyol is 0.04-0.08 wt%, and the ratio of the addition amount of the surface tension regulator to the polyether polyol is 0.5-1.5 wt%.
5. The preparation method of the polyurethane microporous foam with the uniform pore diameter as claimed in any one of claims 1 to 4, is characterized by comprising the following steps:
1) uniformly mixing the component A and the component B to form a mixture AB, and uniformly mixing the component C and the component D to form a mixture CD; wherein the mass ratio of the functional group of the component A to the reactive group of the component B is 1: 1-1.05: 1, the mass ratio of the functional group of the component C to the functional group of the component D is 1: 1-1.05: 1;
2) after the mixture AB stands still, adding the mixture AB into the mixture CD and uniformly mixing to form a mixture ABCD; wherein the ratio of the mixture AB to the mixture CD is 20wt% -40 wt%;
3) coating the mixture ABCD obtained in the step 2) on a PET film, and heating and curing to obtain the polyurethane microporous foam with uniform pore size.
6. The method for preparing the polyurethane microporous foam with the uniform pore diameter as claimed in claim 5, wherein in the step 1), the rotation speed of the component A and the component B is 6000rpm-10000rpm when being mixed, the mixing time is 3s-5s, the rotation speed of the component C and the component D is 6000rpm-10000rpm when being mixed, and the mixing time is 5s-8 s;
the standing time of the mixture AB in the step 2) is 5s-8s, and the standing time of the mixture CD is 4s-6 s;
the mixing time of the mixture AB and the mixture CD is 5s-8s, and the rotating speed is 8000rpm-10000 rpm.
7. The method for preparing the polyurethane microcellular foam with the uniform pore diameter as claimed in claim 5, wherein the coating thickness in the step 3) is 0.1mm to 0.5 mm; the heating curing temperature is 115-120 ℃; the heating curing time is 15-20 min.
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