CN111732830B - Uniform leveling polyurethane multi-component stock solution composition and preparation method thereof - Google Patents
Uniform leveling polyurethane multi-component stock solution composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyurethane raw material, in particular to a polyurethane stock solution, and further in particular relates to a uniform leveling polyurethane multi-component stock solution composition and a preparation method thereof. The polyurethane multicomponent raw liquid composition is characterized by comprising 110 parts by weight of a raw material A, 10-15 parts by weight of a raw material C and 120 parts by weight of a raw material B; the raw material A comprises polyester polyol, a liquid leveling agent, needle-shaped inorganic fibers, a chain extender, a catalyst and a foaming agent; the raw material C comprises a pretreated solid flatting agent and polyether polyol; the raw material B is isocyanate. The invention uses silicone powder, butyl acetate cellulose and polytetrafluoroethylene micropowder, and adopts polyurethane hard foam to cure the silicone powder, butyl acetate cellulose and polytetrafluoroethylene micropowder into the solid leveling agent in advance, so that the solid leveling agent is uniformly dispersed in subsequent stock solution and has good compatibility. The uniform leveling promotes the disappearance of casting surface defects without causing a substantial disappearance of micropores in the cast foamed polyurethane shoe material.
Description
Technical Field
The invention relates to a polyurethane raw material, in particular to a polyurethane stock solution, and further in particular relates to a uniform leveling polyurethane multi-component stock solution composition and a preparation method thereof. In particular to the modification of the stock solution of the polyurethane shoe material.
Background
Polyurethane is a multifunctional and multipurpose synthetic high molecular material, and is generally prepared by reacting oligomer polyol, polyisocyanate, a chain extender and a cross-linking agent. Compared with plastics, the polyurethane has the advantages of high toughness, high wear resistance and the like; compared with rubber, polyurethane has the advantages of wear resistance, cutting resistance, tearing resistance, high bearing property and the like. Because the preparation of the polyurethane can obtain the polyurethane with different forms and performances by controlling raw materials and reaction conditions, the polyurethane has wider application compared with common high polymer materials. Currently, polyurethane has different applications such as polyurethane coating, sealant, adhesive, hard foam, soft foam, thermoplastic elastomer, microcellular elastomer, fiber and the like.
The polyurethane stock solution is a key precursor raw material for preparing polyurethane, is different from macromolecule plastic and rubber with wound pain, is stored in two components or multiple components, and can be poured by quickly mixing the multiple components during preparation of the polyurethane product to obtain the polyurethane products with different shapes. Such as shoe soles, steering wheels of automobiles, truckles, sealing gaskets and the like, and various special-shaped pouring pieces can be directly poured. Compared with the injection molding of plastic rubber, the manufacturing cost of the polyurethane is greatly reduced due to the characteristic of polyurethane pouring forming.
The polyurethane pouring forming shoe sole has the advantages of high speed, high yield, small production environment pollution, high efficiency and energy conservation, and the polyurethane is popularized and used in the field of shoe material preparation in a large scale based on the principle of rapid curing forming after the polyurethane pouring forming. In addition, polyurethane is used as a sole material, has the characteristics of high strength, wear resistance, good elasticity, comfort in wearing and the like, and becomes the first choice of high-grade soles.
With the popularization and use of polyurethane shoe materials, besides polyurethane soles of some high-grade leather shoes and fashion shoes, polyurethane is also widely used for sports shoes, slippers, sneakers and the like, so that the demand of polyurethane stock solution is increased. The cost of polyurethane is higher than that of shoe materials such as PVC, EVA and the like, and in order to avoid the cost problem, various production enterprises generally adopt micro-foaming treatment during pouring reaction forming, and the density of the sole can be controlled to be 0.4-0.5g/cm through the micro-foaming treatment 3 Not only the shoe material is light, but also the elastic buffering effect is improved. At present, the problem that polyurethane occupies the market in the field of shoe materials is that the density of the polyurethane shoe materials is further reduced so as to reduce the costA key. Although the density of the polyurethane shoe material can be significantly reduced by increasing the micro-foaming force, excessive foaming can degrade the polyurethane properties. In the specific production, the water content in the stock solution polyester polyol is controlled to be 0.3-0.4 percent to obtain the density of 0.4-0.5g/cm 3 The sole of (1); in order to obtain a polyurethane shoe material having a lower density, a polyurethane shoe material having a lower density can be obtained by controlling the water content of the polyester polyol in the polyurethane stock solution to 0.7 to 0.8%. However, the severe foaming causes the surface quality of the polyurethane shoe material to be poor, defects such as fish eyes, sand eyes, shrinkage cavities, orange peel and the like are easy to occur, the dimensional stability of the micro-foaming polyurethane elastic shoe material is reduced, the mold release property is poor, and the production efficiency and the product quality are seriously affected.
In order to ensure good demoulding performance and uniform surface quality of shoe materials poured with polyurethane micro-foaming, at present, organic silicon demoulding agents are mostly adopted. Clearly, it is difficult to eliminate surface defects in lower density polyurethane shoe materials by means of release agents alone when developing the shoe materials. Because the two-component or multi-component stock solution is mixed and then cast for forming when the polyurethane shoe material is prepared by casting reaction, the good flowing of the polyurethane stock solution is beneficial to eliminating the quality defect of the surface of the cast polyurethane shoe material.
Disclosure of Invention
At present, when a low-density polyurethane shoe material is developed, the using amount of foaming agent water is increased, so that the density of the polyurethane shoe material can be greatly reduced. However, excessive foaming causes deterioration in the expression quality of the polyurethane shoe material produced after cast molding, and many defects such as large open pores exist. The reasons are mainly that the foaming reaction is severe, and the polyurethane stock solution is difficult to flow better and fill the defects in time. Therefore, the invention provides a uniform leveling polyurethane multi-component stock solution composition, which can flow in time to fill the foaming defect on the surface during casting molding foaming by improving the fluidity and automatic leveling property of the polyurethane stock solution, thereby obtaining a polyurethane shoe material with a high-quality surface; further provides a preparation method of the polyurethane multi-component stock solution.
In order to realize the purpose, firstly, a uniform leveling polyurethane multicomponent stock solution composition is provided, which is characterized in that the polyurethane multicomponent stock solution composition comprises 100 parts by weight of raw material A, 10-15 parts by weight of raw material C and 110 parts by weight of raw material B, 120 parts by weight of raw material B; wherein:
the raw material A comprises the following components in parts by weight: 80-90 parts of polyester polyol with the molecular weight of 2000-3000, 0.5-1 part of liquid leveling agent, 3-5 parts of needle-shaped inorganic fiber, 3-8 parts of chain extender, 0.05-0.1 part of catalyst and 0.6-0.8 part of foaming agent;
the raw material C comprises 20-30 parts by weight of a pretreated solid flatting agent and 40-50 parts by weight of polyether polyol; wherein the pretreated solid leveling agent is prepared by the following method: adding 10-15 parts by weight of silicone powder, 3-5 parts by weight of butyl acetate cellulose and 1-3 parts by weight of polytetrafluoroethylene micro powder into a ball mill, grinding and refining in a dry state, and then uniformly dispersing with 50-60 parts by weight of hard polyether polyol, 1-2 parts by weight of pentamethyl dipropylene triamine and 1-3 parts by weight of cyclopentane; further adding 15-30 parts by weight of polyisocyanate, quickly stirring to form hard bubbles, standing for 24 hours, and then crushing and refining to 200-mesh sieve to obtain a pretreated solid leveling agent;
the raw material B is isocyanate.
Further, a preparation method of the uniform leveling polyurethane multi-component stock solution composition is provided, and is characterized by comprising the following steps:
s1, adding 10-15 parts by weight of silicone powder, 3-5 parts by weight of butyl acetate cellulose and 1-3 parts by weight of polytetrafluoroethylene micro powder into a ball mill for dry grinding and refining, and then uniformly dispersing with 50-60 parts by weight of hard polyether polyol, 1-2 parts by weight of pentamethyl dipropylene triamine and 1-3 parts by weight of cyclopentane; further adding 15-30 parts by weight of polyisocyanate, quickly stirring to form hard bubbles, standing for 24 hours, and then crushing and refining to 200-mesh sieve to obtain a pretreated solid leveling agent;
s2: uniformly dispersing 80-90 parts of polyester polyol with the molecular weight of 2000-3000, 0.2-0.3 part of liquid leveling agent, 3-5 parts of needle-shaped inorganic fiber, 3-8 parts of chain extender, 0.05-0.1 part of catalyst and 0.6-0.8 part of foaming agent to obtain a raw material A;
s3: uniformly mixing 20-30 parts by weight of the pretreated solid leveling agent obtained in the step S1 and 40-50 parts by weight of polyether polyol to obtain a raw material C;
s4, taking isocyanate as a raw material B.
Preferably, the silicone powder in step S1 is a silicone powder of the same general type, which is generally produced by adding silicon dioxide to a higher molecular weight organic silicone, and preferably, the silicone powder has a siloxane content of 40%. The silicone powder can not only improve the demoulding performance of polyurethane pouring moulding, but also obviously improve the smoothness and the self-fluidity of materials, and promote surface leveling in the micro-foaming process and eliminate surface defects when the polyurethane stock solution is poured moulding reaction.
Preferably, the hard polyether polyol in step S1 is a general hard foam polyether polyol using sucrose as an initiator. According to the invention, silicone powder, butyl acetate cellulose and polytetrafluoroethylene micropowder which can promote the flow and leveling of polyurethane stock solution are ground and mixed in advance, and are dispersed in hard polyether polyol, and react with polyisocyanate to generate hard bubbles, and the hard bubbles are easy to crush and refine, so that the silicone powder, the butyl acetate cellulose and the polytetrafluoroethylene micropowder with the leveling function are compounded into the pretreated solid leveling agent. The solid flatting agent is pretreated by the pretreatment of the polyurethane, so that the solid flatting agent is beneficial to being uniformly dispersed in the polyurethane stock solution in the subsequent use; the purpose of forming the hard foam polyurethane is to facilitate the pulverization and refinement.
Preferably, the pulverizing and refining in step S1 is performed by using a conventional pulverizing and refining machine, such as various jet mills.
Preferably, in step S1, the polyisocyanate is diphenylmethane diisocyanate.
Preferably, in step S2, the polyester polyol with molecular weight of 2000-3000 is ethylene glycol, diethylene glycol, 1, 4-butanediol, purified terephthalic acid and purified adipic acid, and the polyesterification reaction is carried out under the action of catalyst tetraisopropyl titanate until the acid value of the polyester polyol reaches 0.2-0.5 and the hydroxyl value reaches 50-60 mgKOH/g.
Preferably, the liquid leveling agent in step S2 is a polyether modified silicone leveling agent.
Preferably, the needle-shaped inorganic fiber in step S2 is at least one selected from needle-shaped wollastonite, needle-shaped calcium carbonate whisker, needle-shaped calcium sulfate whisker and needle-shaped magnesium hydroxide; the acicular inorganic substance has the characteristics of short fiber and is used for enhancing the strength and the wear resistance of polyurethane.
Preferably, the chain extender in step S2 is one of 1, 4-butanediol, ethylene glycol and glycerol.
Preferably, in step S2, the catalyst is at least one of stannous octoate, dibutyl tin dilaurate, and di-n-butyltin diacetate.
Preferably, in step S2, the foaming agent is water and sodium sulfate decahydrate in a mass ratio of 4: 1, when the content of the water in parts by weight is higher, the polyurethane shoe material with lower density can be obtained, however, the foaming is more violent, so the water-containing sodium sulfate decahydrate is used as the foaming agent for supplementing water to reduce the foaming intensity, thereby assisting in reducing the surface quality defects of the polyurethane product.
Preferably, the polyether polyol of step S3 has better fluidity, and is prepared into a slurry by being dispersed with the pretreated solid leveling agent, so as to facilitate the mixing of the raw material C and the raw material A, B in a liquid state.
Preferably, the isocyanate in step S4 is liquefied MDI.
The polyurethane shoe material has the advantages that in the process of raw liquid mixing, pouring and molding, the viscosity of the material is increased along with gradual reaction, so that the leveling of the surface of a product is limited, and orange peel, sand holes, shrinkage holes and other defects are easily formed. The hard foam is easy to crush and refine, so that the hard foam polyurethane is formed, and the purpose is to be more favorable for crushing and refining; the solid flatting agent is pretreated by the pretreatment of the polyurethane, so that the solid flatting agent is favorably and uniformly dispersed in the polyurethane stock solution in the subsequent use. Different from the traditional liquid leveling agent, the silicone powder, the butyl acetate cellulose and the polytetrafluoroethylene micro powder are finally dispersed in the polyurethane shoe material in a micro-particle state, and the polyurethane hard foam is used for curing treatment in advance, so that the polyurethane shoe material is uniformly dispersed in subsequent stock solution and has good compatibility. Furthermore, the polyether modified organic silicon leveling agent is used in the raw material A, the pretreated solid leveling agent is used in the raw material C, when the raw materials are mixed in a liquid state before original liquid pouring, the polyether modified organic silicon leveling agent is the most conventional liquid leveling agent to eliminate the surface defects of the pouring liquid, the reaction is carried out after the pouring, the micro-foaming viscosity of the materials in the molding process is gradually increased, and the pretreated solid leveling agent dispersed in the materials promotes the disappearance of the surface defects without causing the disappearance of micropores in the polyurethane shoe materials subjected to pouring foaming. Thereby obtaining the polyurethane shoe material with good surface quality.
It is known that the use of leveling agents in coating materials results in uniform flow of the coating surface, uniform leveling of the formed coating, and defoaming of the cells in the coating material. The invention uses the leveling agent for reference to ensure that the surface of polyurethane flows uniformly when pouring and foaming so as to eliminate the quality defects of orange peel, sand holes and the like. However, in order to prevent the micropores in the polyurethane stock solution from being defoamed, the invention adopts the solid leveling agent which is pretreated by polyurethane, and the pretreated solid leveling agent promotes the disappearance of surface defects without causing the disappearance of a large amount of micropores in the polyurethane shoe material which is poured and foamed.
In an initial experiment, more liquid leveling agents are directly added into a raw material A, and the liquid leveling agents and a raw material B are cast and formed in a molding process, so that the surface quality of a shoe material formed by casting reaction is excellent, the defects of orange peel, sand holes and the like are avoided, however, the density of the shoe material is high, and a large number of micro-pores are eliminated under the influence of the leveling agents. Based on the above, the leveling agent is subjected to curing and compounding treatment in advance, and is used as a powder filler in a poured polyurethane stock solution to promote the disappearance of the surface defects of the polyurethane shoe material without seriously affecting micropores in the poured and foamed polyurethane shoe material.
Compared with the prior art, the invention has the following excellent effects:
(1) in the prior art, when the cost of polyurethane shoe materials is reduced, the cost is reduced by increasing foaming and reducing density, but the surface of a foamed polyurethane product has the defects of orange peel, sand holes and the like, so that the product quality is influenced.
(2) The invention uses silicone powder, butyl acetate cellulose and polytetrafluoroethylene micropowder, and adopts polyurethane hard foam to cure the silicone powder, butyl acetate cellulose and polytetrafluoroethylene micropowder into the solid leveling agent in advance, so that the solid leveling agent is uniformly dispersed in subsequent stock solution and has good compatibility. Promote the disappearance of the defects on the casting surface without causing the micropores in the casting foamed polyurethane shoe material to disappear in a large amount. So that the leveling and the micro-foaming are simultaneously achieved.
(3) The preparation method is simple, the preparation of the pretreated solid leveling agent is completely modified by using the existing equipment of polyurethane manufacturers, only crushing equipment is needed, and the preparation method is suitable for large-scale popularization and application.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a photograph of a pattern of a polyurethane shoe sole after microcellular foaming, obtained from a multi-component stock solution according to the embodiment of example 1 of the present invention, for cast molding.
FIG. 2 is a photograph of a polyurethane shoe sole pattern after microcellular foaming, using the multi-component dope obtained according to the embodiment of comparative example 1 for cast molding.
Detailed Description
As the raw material used in the present invention, a commercially available product can be used, unless otherwise specified. The present invention is further illustrated by the following specific examples, which are not intended to limit the invention, but are to be construed as being limited thereto.
Example one
S1, adding 15 parts by weight of silicone powder, 3 parts by weight of butyl acetate cellulose and 2 parts by weight of polytetrafluoroethylene micropowder into a ball mill, grinding for 3 hours in a dry state by taking zirconia balls as grinding agents to obtain ground and ground products, and then uniformly dispersing the ground and ground products with 50 parts by weight of sucrose polyether polyol, 1 part by weight of pentamethyl dipropylene triamine and 2 parts by weight of cyclopentane; further adding 15 parts by weight of diphenylmethane diisocyanate, rapidly stirring to form hard bubbles, aging for 24 hours, and grinding and refining by a vortex jet mill until the mixture passes through a 200-mesh sieve to obtain a pretreated solid leveling agent;
s2: 80 parts of polyester polyol with the molecular weight of 2000, 0.2 part of polyether modified organic silicon flatting agent, 5 parts of needle-shaped wollastonite, 5 parts of chain extender 1, 4-butanediol, 0.05 part of catalyst stannous octoate, water and sodium sulfate decahydrate in a mass ratio of 4: 1, dispersing 0.7 part of the mixture uniformly to obtain a raw material A;
s3: uniformly mixing 20 parts by weight of the pretreated solid flatting agent obtained in the step S1 and 40 parts by weight of polytetrahydrofuran ether polyol to obtain a raw material C;
and S4, taking the liquefied MDI as a raw material B.
Mixing the raw material A100 weight parts and the raw material C15 weight parts at high speed for 10min, mixing with the raw material B110 weight parts at 1000rpm for 20s, uniformly injecting into a metal shoe material mould with fine lines, foaming and curing at 80 ℃ for 10min, and demoulding to obtain the sole as shown in figure 1, wherein the fine lines are uniform and have no obvious defects.
Example two
S1, adding 10 parts by weight of silicone powder, 3 parts by weight of butyl acetate cellulose and 2 parts by weight of polytetrafluoroethylene micropowder into a ball mill, grinding for 1 hour in a dry state by taking zirconia balls as grinding agents to obtain ground and ground products, and then uniformly dispersing the ground and ground products with 50 parts by weight of sucrose polyether polyol, 1 part by weight of pentamethyl dipropylene triamine and 2 parts by weight of cyclopentane; further adding 15 parts by weight of diphenylmethane diisocyanate, rapidly stirring to form hard bubbles, aging for 24 hours, and grinding and refining by a vortex jet mill until the mixture passes through a 200-mesh sieve to obtain a pretreated solid leveling agent;
s2: 80 parts of polyester polyol with the molecular weight of 2000, 0.2 part of polyether modified organic silicon flatting agent, 5 parts of needle-shaped wollastonite, 8 parts of chain extender 1, 4-butanediol, 0.05 part of catalyst stannous octoate, water and sodium sulfate decahydrate in a mass ratio of 4: 1, dispersing 0.6 part of the mixture uniformly to obtain a raw material A;
s3: uniformly mixing 20 parts by weight of the pretreated solid flatting agent obtained in the step S1 and 50 parts by weight of polytetrahydrofuran ether polyol to obtain a raw material C;
and S4, taking the liquefied MDI as the raw material B.
Mixing the raw material A100 weight parts and the raw material C10 weight parts at high speed for 10min, then mixing with the raw material B110 weight parts at high speed for 20s at 1000rpm, uniformly injecting into a metal shoe material mould with fine lines, foaming and curing at 80 ℃ for 10min, and demoulding to obtain the sole.
EXAMPLE III
S1, adding 10 parts by weight of silicone powder, 5 parts by weight of butyl acetate cellulose and 2 parts by weight of polytetrafluoroethylene micropowder into a ball mill, grinding for 2 hours in a dry state by taking zirconia balls as grinding agents to obtain ground and ground products, and then uniformly dispersing the ground and ground products with 50 parts by weight of sucrose polyether polyol, 1 part by weight of pentamethyl dipropylene triamine and 2 parts by weight of cyclopentane; further adding 15 parts by weight of diphenylmethane diisocyanate, rapidly stirring to form hard bubbles, aging for 24 hours, and grinding and refining by a vortex jet mill until the mixture passes through a 200-mesh sieve to obtain a pretreated solid leveling agent;
s2: 80 parts of polyester polyol with the molecular weight of 2000, 0.2 part of polyether modified organic silicon flatting agent, 3 parts of needle-shaped magnesium hydroxide, 8 parts of chain extender glycerol, 0.08 part of catalyst stannous octoate, water and sodium sulfate decahydrate in a mass ratio of 4: 1, dispersing 0.8 part of the mixture uniformly to obtain a raw material A;
s3: uniformly mixing 20 parts by weight of the pretreated solid flatting agent obtained in the step S1 and 50 parts by weight of polytetrahydrofuran ether polyol to obtain a raw material C;
and S4, taking the liquefied MDI as the raw material B.
Stirring and mixing 110 parts by weight of the raw material A and 15 parts by weight of the raw material C at a high speed for 10min, then mixing with 120 parts by weight of the raw material B at a high speed for 20s at 1000rpm, uniformly injecting into a metal shoe material mould with fine lines, foaming and curing at 80 ℃ for 10min, and demoulding to obtain the sole.
Comparative example 1
S1, mixing 80 parts of polyester polyol with the molecular weight of 2000, 0.2 part of polyether modified organic silicon flatting agent, 5 parts of needle-shaped wollastonite, 5 parts of chain extender 1, 4-butanediol, 0.05 part of catalyst stannous octoate, water and sodium sulfate decahydrate in a mass ratio of 4: 1, dispersing 0.7 part of the mixture uniformly to obtain a raw material A;
s2: taking polytetrahydrofuran ether polyol as a raw material C;
and S3, taking the liquefied MDI as the raw material B.
Mixing the raw material A100 parts by weight and the raw material C15 parts by weight at a high speed for 10min, then mixing the mixture with the material B110 parts by weight at a high speed of 1000rpm for 20s, uniformly injecting the mixture into a metal shoe material mould with fine lines, foaming and curing the mixture at 80 ℃ for 10min, and demoulding to obtain the sole which has more surface defects, poor fine line precision and the phenomena of sand holes and orange peel as shown in figure 2.
Comparative example No. two
S1, adding 10 parts by weight of silicone powder, 3 parts by weight of butyl acetate cellulose and 2 parts by weight of polytetrafluoroethylene micro powder into a ball mill, grinding for 1 hour in a dry state by taking zirconia balls as grinding agents to obtain ground powder, and then uniformly dispersing the ground powder with 50 parts by weight of sucrose polyether polyol, 1 part by weight of pentamethyl dipropylene triamine and 2 parts by weight of cyclopentane; further adding 15 parts by weight of diphenylmethane diisocyanate, rapidly stirring to form hard bubbles, aging for 24 hours, and grinding and refining by a vortex jet mill until the mixture passes through a 200-mesh sieve to obtain a pretreated solid leveling agent;
s2: uniformly dispersing 80 parts of polyester polyol with the molecular weight of 2000, 0.2 part of polyether modified organic silicon flatting agent, 5 parts of needle-shaped wollastonite, 8 parts of chain extender 1, 4-butanediol, 0.05 part of catalyst stannous octoate and 0.6 part of water to obtain a raw material A;
s3: uniformly mixing 20 parts by weight of the pretreated solid flatting agent obtained in the step S1 and 50 parts by weight of polytetrahydrofuran ether polyol to obtain a raw material C;
and S4, taking the liquefied MDI as the raw material B.
Mixing the raw material A100 weight parts and the raw material C10 weight parts at high speed for 10min, then mixing with the raw material B110 weight parts at high speed for 20s at 1000rpm, uniformly injecting into a metal shoe material mould with fine lines, foaming and curing at 80 ℃ for 10min, and demoulding to obtain the sole.
The foaming agent adopts water, and sodium sulfate decahydrate is not matched, so that the foaming is violent, and the surface uniformity of the polyurethane product is influenced.
Comparative example No. three
S1, adding 10 parts by weight of silicone powder, 5 parts by weight of butyl acetate cellulose and 2 parts by weight of polytetrafluoroethylene micropowder into a ball mill, grinding for 2 hours in a dry state by taking zirconia balls as grinding agents to obtain ground and ground products, and then uniformly dispersing the ground and ground products with 50 parts by weight of sucrose polyether polyol, 1 part by weight of pentamethyl dipropylene triamine and 2 parts by weight of cyclopentane; further adding 15 parts by weight of diphenylmethane diisocyanate, rapidly stirring to form hard bubbles, aging for 24 hours, and grinding and refining by a vortex jet mill until the mixture passes through a 200-mesh sieve to obtain a pretreated solid leveling agent;
s2: 80 parts of polyester polyol with the molecular weight of 2000, 0.2 part of polyether modified organic silicon flatting agent, 8 parts of chain extender glycerol, 0.08 part of catalyst stannous octoate, water and sodium sulfate decahydrate in a mass ratio of 4: 1, dispersing 0.8 part of the mixture uniformly to obtain a raw material A;
s3: uniformly mixing 20 parts by weight of the pretreated solid flatting agent obtained in the step S1 and 50 parts by weight of polytetrahydrofuran ether polyol to obtain a raw material C;
and S4, taking the liquefied MDI as the raw material B.
Stirring and mixing 110 parts by weight of the raw material A and 15 parts by weight of the raw material C at a high speed for 10min, then mixing with 120 parts by weight of the raw material B at a high speed for 20s at 1000rpm, uniformly injecting into a metal shoe material mould with fine lines, foaming and curing at 80 ℃ for 10min, and demoulding to obtain the sole.
The strength of the polyurethane product formed by pouring and molding is reduced to a certain extent without using needle-like inorganic substances.
Comparative example No. four
S1, adding 15 parts by weight of silicone powder, 3 parts by weight of butyl acetate cellulose and 2 parts by weight of polytetrafluoroethylene micropowder into a ball mill, grinding for 3 hours in a dry state by taking zirconia balls as grinding agents to obtain ground and ground substances, and sieving by a 200-mesh sieve to obtain the pretreated solid leveling agent;
s2: 80 parts of polyester polyol with the molecular weight of 2000, 0.2 part of polyether modified organic silicon flatting agent, 5 parts of needle-shaped wollastonite, 5 parts of chain extender 1, 4-butanediol, 0.05 part of catalyst stannous octoate, water and sodium sulfate decahydrate in a mass ratio of 4: 1, dispersing 0.7 part of the mixture uniformly to obtain a raw material A;
s3: uniformly mixing 20 parts by weight of the pretreated solid flatting agent obtained in the step S1 and 40 parts by weight of polytetrahydrofuran ether polyol to obtain a raw material C;
and S4, taking the liquefied MDI as the raw material B.
Stirring and mixing 100 parts by weight of the raw material A and 5 parts by weight of the raw material C at a high speed for 10min, then mixing with 110 parts by weight of the raw material B at a high speed of 1000rpm for 20s, uniformly injecting into a metal shoe material mould with fine lines, foaming and curing at 80 ℃ for 10min, and demoulding.
Since the silicone powder, the butyl acetate cellulose and the polytetrafluoroethylene micro powder are directly compounded, the dispersion and the compatibility of the flatting agent in the stock solution are influenced without utilizing the pretreatment of the hard foam polyurethane, and the flatting promoting effect of the flatting agent is influenced.
And (3) sample testing:
the shoe materials obtained in examples 1 to 3 and comparative examples 1 to 3 were placed in a unified manner for 24 hours and then used as test samples to conduct a test of basic performance.
1. Molded density test:
the density was measured by test method A with reference to GB/T533-.
2. And (3) testing tensile strength:
with reference to GB/T6344-2008 "determination of tensile Strength and elongation at Break of Flexible foamed Polymer Material", at least 5 dumbbell-shaped test pieces were cut out with a prototype at a tensile rate of 500. + -.50 mm/mm, and the tensile strength and elongation tested are shown in Table 1.
Table 1:
through the tests, the foaming strength is increased, the polyurethane casting molding product with lower density is obtained, and meanwhile, the liquid leveling agent and the solid leveling agent are used in a coordinated manner, so that the polyurethane stock solution has good uniform leveling property during casting molding, and the defect of the surface of the cast polyurethane product is eliminated. Not only ensures the appearance quality of the product, but also well maintains the basic mechanical property. The method has great significance for enterprises in reducing cost and ensuring quality.
It is to be understood that the exemplary embodiments are to be considered as illustrative and not restrictive. Moreover, descriptions of features or aspects in various embodiments should be applicable to other similar features or aspects in other embodiments. In the specific production implementation, pigments, antioxidants, anti-aging agents and the like can be added according to the conventional requirements. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (9)
1. The uniform leveling polyurethane multi-component stock solution composition is characterized by comprising 110 parts by weight of a raw material A, 10-15 parts by weight of a raw material C and 120 parts by weight of a raw material B; wherein:
the raw material A comprises the following components in parts by weight: 80-90 parts of polyester polyol with the molecular weight of 2000-3000, 0.5-1 part of liquid leveling agent, 3-5 parts of needle-shaped inorganic fiber, 3-8 parts of chain extender, 0.05-0.1 part of catalyst and 0.6-0.8 part of foaming agent; the foaming agent is water and sodium sulfate decahydrate in a mass ratio of 4: 1;
the raw material C comprises 20-30 parts by weight of a pretreated solid flatting agent and 40-50 parts by weight of polyether polyol; wherein the pretreated solid leveling agent is prepared by the following method: adding 10-15 parts by weight of silicone powder, 3-5 parts by weight of butyl acetate cellulose and 1-3 parts by weight of polytetrafluoroethylene micropowder into a ball mill for dry grinding and refining, and uniformly dispersing with 50-60 parts by weight of hard polyether polyol, 1-2 parts by weight of pentamethyl dipropylene triamine and 1-3 parts by weight of cyclopentane; further adding 15-30 parts by weight of polyisocyanate, quickly stirring to form hard bubbles, standing for 24 hours, and then crushing and refining to 200-mesh sieve to obtain a pretreated solid leveling agent;
the raw material B is isocyanate.
2. A method for preparing the uniform leveling polyurethane multicomponent dope composition of claim 1, wherein the method comprises the following steps:
s1, adding 10-15 parts by weight of silicone powder, 3-5 parts by weight of butyl acetate cellulose and 1-3 parts by weight of polytetrafluoroethylene micro powder into a ball mill for dry grinding and refining, and then uniformly dispersing with 50-60 parts by weight of hard polyether polyol, 1-2 parts by weight of pentamethyl dipropylene triamine and 1-3 parts by weight of cyclopentane; further adding 15-30 parts by weight of polyisocyanate, quickly stirring to form hard bubbles, standing for 24 hours, and then crushing and refining to 200-mesh sieve to obtain a pretreated solid leveling agent;
s2: uniformly dispersing 80-90 parts of polyester polyol with the molecular weight of 2000-3000, 0.2-0.3 part of liquid leveling agent, 3-5 parts of needle-shaped inorganic fiber, 3-8 parts of chain extender, 0.05-0.1 part of catalyst and 0.6-0.8 part of foaming agent to obtain a raw material A;
s3: uniformly mixing 20-30 parts by weight of the pretreated solid leveling agent obtained in the step S1 and 40-50 parts by weight of polyether polyol to obtain a raw material C;
and S4, taking isocyanate as a raw material B.
3. The method of preparing a homogeneous, leveling polyurethane multicomponent dope composition of claim 2, wherein: in step S1, general hard foam polyether polyol using sucrose as an initiator is selected as the hard polyether polyol.
4. The method of preparing a homogeneous, leveling polyurethane multicomponent dope composition of claim 2, wherein: in step S1, the polyisocyanate is diphenylmethane diisocyanate.
5. The method of preparing a homogeneous, leveling polyurethane multicomponent dope composition of claim 2, wherein: in step S2, the polyester polyol with molecular weight of 2000-3000 is prepared by performing polyesterification reaction of ethylene glycol, diethylene glycol, 1, 4-butanediol, purified terephthalic acid and purified adipic acid under the action of a catalyst tetraisopropyl titanate until the acid value of the polyester polyol reaches 0.2-0.5 and the hydroxyl value reaches 50-60 mgKOH/g.
6. The method of preparing a homogeneous, leveling polyurethane multicomponent dope composition of claim 2, wherein: and S2, selecting polyether modified organic silicon flatting agent as the liquid flatting agent.
7. The method of preparing a uniform leveling polyurethane multicomponent dope composition according to claim 2, wherein: the needle-shaped inorganic fiber is at least one of needle-shaped wollastonite, needle-shaped calcium carbonate whiskers, needle-shaped calcium sulfate whiskers and needle-shaped magnesium hydroxide.
8. The method of preparing a homogeneous, leveling polyurethane multicomponent dope composition of claim 2, wherein: one of 1, 4-butanediol, ethylene glycol and glycerol serving as chain extenders; the catalyst is at least one of stannous octoate, dibutyl tin dilaurate and di-n-butyltin diacetate.
9. The method of preparing a homogeneous, leveling polyurethane multicomponent dope composition of claim 2, wherein: and step S4, the isocyanate is liquefied MDI.
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| WO1999016816A1 (en) * | 1997-09-29 | 1999-04-08 | Exxon Chemical Patents Inc. | A method for forming integral skin flexible foams from high purity cyclopentane and blend thereof |
| CN101067039A (en) * | 2006-11-17 | 2007-11-07 | 刘畅 | Process of producing sound absorbing material with waste polyurethane foam |
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