CN111019329A - Shoe pad and preparation process thereof - Google Patents
Shoe pad and preparation process thereof Download PDFInfo
- Publication number
- CN111019329A CN111019329A CN201911352619.8A CN201911352619A CN111019329A CN 111019329 A CN111019329 A CN 111019329A CN 201911352619 A CN201911352619 A CN 201911352619A CN 111019329 A CN111019329 A CN 111019329A
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- China
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- parts
- polyurethane
- insole
- bismaleimide
- solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of insoles, and discloses an insole which comprises the following components in parts by weight: 80-100 parts of polyurethane; 6-15 parts of bismaleimide; 3-4 parts of terephthalaldehyde; 2-3 parts of magnesium oxide; 8-10 parts of a solvent; 1-2 parts of a plasticizer; 1-2 parts of a curing agent. The invention has the following advantages and effects: terephthalaldehyde is taken as a cross-linking agent, and polyurethane and bismaleimide are mixed with a solvent and cross-linked to form a stable net-shaped cross-linked network, so that the polyurethane composite insole with a compact structure and a stable molecular chain is obtained; terephthalaldehyde and bismaleimide have a synergistic effect, amide carbonylation reaction can occur under the action of a solvent, and are mixed with polyurethane, so that soft segments and hard segments in a polyurethane molecular chain are arranged more compactly, the structural stability is improved, the damage of heat energy, radiation energy, water molecules and the like to the polyurethane molecular chain is prevented, and the anti-aging performance of the polyurethane insole is improved.
Description
Technical Field
The invention relates to the technical field of insoles, in particular to an insole and a preparation process thereof.
Background
Polyurethane resin comprises elastomers, foams, coatings, fibers and the like, is widely applied to the petroleum industry, the automobile industry, the aerospace industry and the like, is visible everywhere in all aspects of people's life, and insoles are closely related to people's life. However, the conventional insole is generally a cloth insole, so that the comfort level is low and the elasticity is poor. The polyurethane insole is more and more popular among people because of comfort and durability.
Currently, patent publication No. CN109180905A discloses a highly elastic polyurethane insole with low compression deformation and a preparation method thereof. The weight ratio of 100: 70-90 of a component A and a component B; the component A is prepared from the following raw materials: polyether polyol, polytetrahydrofuran polyol, polymer polyether polyol, a foam stabilizer, a high-activity silane stabilizer, a cross-linking agent, a chain extender, a foaming agent and a delayed catalyst, wherein the cross-linking agent consists of a cross-linking agent A and tetrafunctionality polyether polyol NT 403; the component B is prepared from the following raw materials: polyether polyol, diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate and small molecule alcohol.
The above prior art solutions have the following drawbacks: the insole is mainly high in elasticity, the problem of mildew of the conventional insole is solved by frequently airing the insole due to the fact that the conventional insole is easy to mildew in a humid use environment in the use process, and the conventional insole is easily aged due to the exposure of sunlight or the influence of an external environment in airing, so that the performance of the conventional insole is still to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an insole, which can improve the condition that the insole is easily aged due to the exposure of sunlight or the influence of the external environment when being aired.
In order to achieve the purpose, the invention provides the following technical scheme:
an insole comprises the following components in parts by weight:
80-100 parts of polyurethane;
6-15 parts of bismaleimide;
3-4 parts of terephthalaldehyde;
2-3 parts of magnesium oxide;
8-10 parts of a solvent;
1-2 parts of a plasticizer;
1-2 parts of a curing agent.
By adopting the technical scheme, terephthalaldehyde is added as a cross-linking agent, and a solvent is matched, so that polyurethane and bismaleimide are cross-linked to form a stable net-shaped cross-linked network, and therefore the polyurethane composite insole with a compact structure and a stable molecular chain can be obtained, and the anti-aging performance of the polyurethane insole is improved; the terephthalaldehyde and the bismaleimide have a synergistic effect, amide carbonylation reaction can occur under the action of a solvent, and the terephthalaldehyde, the bismaleimide and the polyurethane are mixed, so that the arrangement of a soft segment and a hard segment in a polyurethane molecular chain is more compact, the structural stability is improved, the damage of heat energy, radiation energy, water molecules and the like to the polyurethane molecular chain is prevented, and the anti-aging performance of the polyurethane insole is improved; the addition of magnesium oxide can further improve the hot air aging resistance.
The present invention in a preferred example may be further configured to: the bismaleimide accounts for 10-12% of the polyurethane by weight.
By adopting the technical scheme, experiments prove that the polyurethane insole has better aging resistance when the weight part of the bismaleimide accounts for 10-12% of the weight part of the polyurethane.
The present invention in a preferred example may be further configured to: the calcium sulfate powder also comprises 1-2 parts of calcium sulfate according to parts by weight.
By adopting the technical scheme, the processing performance of the insole is influenced by the addition of the magnesium oxide, and the processing performance of the insole is improved by the synergistic effect of the calcium sulfate and the magnesium oxide, so that the overall performance of the insole is better.
The present invention in a preferred example may be further configured to: according to the parts by weight, the composite material also comprises 1-2 parts of nitrated lignin and 0.4-0.6 part of 1, 4-butanediol.
By adopting the technical scheme, the polyurethane insole has elasticity due to the addition of the nitrolignin and the chain extender, can completely recover deformation, and is more comfortable to wear.
The present invention in a preferred example may be further configured to: the plasticizer is dioctyl sebacate.
By adopting the technical scheme, the plasticizer enhances the flexibility of the polyurethane insole, and the polyurethane insole is easy to process; the dioctyl sebacate can generate a synergistic effect with the nitrolignin and the 1, 4-butanediol when being added as a plasticizer, and the ageing resistance of the mixed component is enhanced while the elasticity is enhanced.
The present invention in a preferred example may be further configured to: the solvent is acetone.
By adopting the technical scheme, blocky lignin particles can not appear when the nitrated lignin, the acetone and the polyurethane are mixed, and the blocky lignin is easily separated out when the used solvent is tetrahydrofuran, so the acetone is selected to be used in the invention.
The present invention in a preferred example may be further configured to: 0.6 to 0.8 portion of age inhibitor SP-C.
By adopting the technical scheme, the protective film has good protective effects on heat aging resistance, flex resistance, light resistance, weather aging resistance and the like.
The second purpose of the invention is to provide a preparation process of the insole with the aging resistance.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation process of insoles comprises the following steps:
s1, mixing polyurethane, bismaleimide, terephthalaldehyde and a solvent, stirring for 1-2 hours at the temperature of 80-90 ℃, then cooling to 50-55 ℃, adding magnesium oxide, a plasticizer and an anti-aging agent SP-C, and stirring for reaction for 2-3 hours to obtain a mixed component;
s2, adding the curing agent into the mixed component of S1, uniformly stirring, pouring into a mold preheated to 45-50 ℃, curing for 30-50min after mold closing, and performing hot press molding according to the size requirement after mold opening to obtain the finished product insole.
By adopting the technical scheme, the raw materials are mixed and then are cured and molded to obtain the finished insole.
The present invention in a preferred example may be further configured to: after the temperature of the S1 is reduced to 50-55 ℃, calcium sulfate, nitrolignin and 1, 4-butanediol can be added.
By adopting the technical scheme, the calcium sulfate is further added, so that the calcium sulfate and the magnesium oxide can generate a synergistic effect; the nitrolignin, the 1, 4-butanediol and the dioctyl sebacate can generate a synergistic effect, so that the anti-aging performance of the polyurethane insole is improved.
In summary, the invention includes at least one of the following beneficial technical effects:
1. adding terephthalaldehyde serving as a cross-linking agent, and matching with a solvent to enable polyurethane and bismaleimide to be cross-linked to form a stable net-shaped cross-linked network, so that a polyurethane composite insole with a compact structure and a stable molecular chain can be obtained, and the anti-aging performance of the polyurethane insole is improved; the terephthalaldehyde and the bismaleimide have a synergistic effect, amide carbonylation reaction can occur under the action of a solvent, and the terephthalaldehyde, the bismaleimide and the polyurethane are mixed, so that the arrangement of a soft segment and a hard segment in a polyurethane molecular chain is more compact, the structural stability is improved, the damage of heat energy, radiation energy, water molecules and the like to the polyurethane molecular chain is prevented, and the anti-aging performance of the polyurethane insole is improved;
2. the addition of the magnesium oxide can further improve the hot air aging resistance, and the calcium sulfate and the magnesium oxide are further added to generate a synergistic effect, so that the problem that the addition of the magnesium oxide influences the processing performance of the insole is solved, and the overall performance of the insole is better;
3. the addition of the nitrolignin and the chain extender enables the polyurethane insole to have elasticity, can completely recover deformation and is more comfortable to wear, and the dioctyl sebacate can generate a synergistic effect with the nitrolignin and the 1, 4-butanediol while being added as a plasticizer, so that the elasticity of the mixed component is improved, and the ageing resistance is enhanced.
Drawings
FIG. 1 is a flow chart of the manufacturing process of the insole of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Examples
Example 1
Referring to fig. 1, the preparation process of the insole disclosed by the invention comprises the following steps:
s1, mixing polyurethane, bismaleimide, terephthalaldehyde and a solvent, stirring for 1h at 80 ℃, then cooling to 50 ℃, adding magnesium oxide, calcium sulfate, nitrolignin, 1, 4-butanediol, a plasticizer and an anti-aging agent SP-C, and stirring for reaction for 2h to obtain a mixed component;
s2, adding the curing agent into the mixed component of S1, uniformly stirring, pouring into a mold, curing for 30min after mold closing, and performing hot press molding according to the size requirement after mold opening to obtain the finished product insole.
In example 1, the weight portion of bismaleimide is 10% of the weight portion of polyurethane, and the content of each component is shown in table 1 below.
Example 2
Referring to fig. 1, the preparation process of the insole disclosed by the invention comprises the following steps:
s1, mixing polyurethane, bismaleimide, terephthalaldehyde and a solvent, stirring for 1-2 hours at 90 ℃, then cooling to 55 ℃, adding magnesium oxide, calcium sulfate, nitrolignin, 1, 4-butanediol, a plasticizer and an anti-aging agent SP-C, and stirring for reaction for 3 hours to obtain a mixed component;
s2, adding the curing agent into the mixed component of S1, uniformly stirring, pouring into a mold, curing for 50min after mold closing, and performing hot press molding according to the size requirement after mold opening to obtain the finished product insole.
In example 2, the weight portion of bismaleimide accounts for 12% of the weight portion of polyurethane, and the content of each component is shown in table 1 below.
Example 3
Referring to fig. 1, the preparation process of the insole disclosed by the invention comprises the following steps:
s1, mixing polyurethane, bismaleimide, terephthalaldehyde and a solvent, stirring for 1-2 hours at 86 ℃, then cooling to 52 ℃, adding magnesium oxide, calcium sulfate, nitrolignin, 1, 4-butanediol, a plasticizer and an anti-aging agent SP-C, and stirring for reaction for 3 hours to obtain a mixed component;
s2, adding the curing agent into the mixed component of S1, uniformly stirring, pouring into a mold, curing for 44min after mold closing, and performing hot press molding according to the size requirement after mold opening to obtain the finished product insole.
In example 3, the weight part of bismaleimide accounts for 11% of the weight part of polyurethane, and the content of each component is shown in table 1 below.
Comparative example 1
The difference from example 1 is that only polyurethane, plasticizer, curing agent and antioxidant SP-C were added, and the contents of each component are shown in Table 2 below.
Comparative example 2
The difference from example 1 is that bismaleimide was replaced with an epoxy resin, and the contents of the respective components are shown in table 2 below.
Comparative example 3
The difference from example 1 is that terephthalaldehyde was replaced with glyoxal, and the contents of each component are shown in table 2 below.
Comparative example 4
The difference from example 1 is that the weight portion of bismaleimide is 7% of the weight portion of polyurethane, and the content of each component is shown in table 2 below.
Comparative example 5
The difference from example 1 is that the weight portion of bismaleimide is 14% of the weight portion of polyurethane, and the content of each component is shown in table 2 below.
Comparative example 6
The difference from example 1 is that magnesium oxide was not added and the contents of the respective components are shown in table 2 below.
Comparative example 7
The difference from example 1 is that calcium sulfate and magnesium oxide were not added and the contents of the respective components are shown in table 2 below.
Comparative example 8
The difference from example 1 is that the plasticizer was replaced with phthalate and the contents of the respective components are shown in table 2 below.
Comparative example 9
The difference from example 1 is that no plasticizer is added and the contents of the components are shown in table 2 below.
Comparative example 10
The difference from example 1 is that no plasticizer, nitrated lignin and 1, 4-butanediol were added and the contents of the components are shown in table 2 below.
TABLE 1 ingredient content Table for each example
TABLE 2 ingredient content in each proportion
Performance test
Testing the mechanical property according to the national standard GB/T1040-92, and performing a test at room temperature, wherein the stretching speed is 500 mm/min; placing the sample in a hot air aging oven, setting the temperature to be 175 ℃, aging for 96 hours, taking out the sample for cooling, testing mechanical performance indexes such as tensile strength, tearing strength and the like after aging to represent the aging resistant condition, wherein the larger the change rate is, the worse the aging resistant performance is, and the test results are shown in the following table 3.
TABLE 3 ageing resistance test results of examples and comparative examples
In summary, the following conclusions can be drawn:
1. as can be seen from a comparison of example 1 and comparative example 1, the anti-aging properties of the polyurethane insole can be significantly improved by mixing the components of the present invention.
2. As can be seen from the comparison between example 1 and comparative examples 2 to 3, bismaleimide and terephthalaldehyde have a synergistic effect, and the simultaneous addition of both is advantageous in improving the anti-aging properties of the polyurethane insole.
3. As can be seen from the comparison of examples 1-3 and comparative examples 4-5, the polyurethane insole has better aging resistance when bismaleimide accounts for 10-12% of the weight of the polyurethane.
4. As can be seen from a comparison of example 1 and comparative examples 6-7, the addition of magnesium oxide and calcium sulfate provides a synergistic effect that improves the aging resistance of the polyurethane insole.
5. As can be seen from the comparison of example 1 and comparative examples 8 to 10, dioctyl sebacate, nitrated lignin and 1, 4-butanediol have a synergistic effect, which is advantageous for improving the anti-aging properties of polyurethane insoles.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (9)
1. An insole, characterized by: the composition comprises the following components in parts by weight:
80-100 parts of polyurethane;
6-15 parts of bismaleimide;
3-4 parts of terephthalaldehyde;
2-3 parts of magnesium oxide;
8-10 parts of a solvent;
1-2 parts of a plasticizer;
1-2 parts of a curing agent.
2. An insole according to claim 1, wherein: the weight portion of the bismaleimide accounts for 10-12% of the weight portion of the polyurethane.
3. An insole according to claim 2, wherein: the calcium sulfate powder also comprises 1-2 parts of calcium sulfate according to parts by weight.
4. An insole according to claim 1, wherein: according to the parts by weight, the composite material also comprises 1-2 parts of nitrated lignin and 0.4-0.6 part of 1, 4-butanediol.
5. An insole according to claim 4, wherein: the plasticizer is dioctyl sebacate.
6. An insole according to claim 1, wherein: the solvent is acetone.
7. An insole according to claim 1, wherein: 0.6 to 0.8 portion of age inhibitor SP-C.
8. A process for the preparation of an insole according to any one of claims 1 to 7, wherein: the method comprises the following steps:
s1, mixing polyurethane, bismaleimide, terephthalaldehyde and a solvent, stirring for 1-2 hours at the temperature of 80-90 ℃, then cooling to 50-55 ℃, adding magnesium oxide, a plasticizer and an anti-aging agent SP-C, and stirring for reaction for 2-3 hours to obtain a mixed component;
s2, adding the curing agent into the mixed component of S1, uniformly stirring, pouring into a mold preheated to 45-50 ℃, curing for 30-50min after mold closing, and performing hot press molding according to the size requirement after mold opening to obtain the finished product insole.
9. The process for preparing an insole according to claim 8, wherein: after the temperature of the S1 is reduced to 50-55 ℃, calcium sulfate, nitrolignin and 1, 4-butanediol can be added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911352619.8A CN111019329A (en) | 2019-12-25 | 2019-12-25 | Shoe pad and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911352619.8A CN111019329A (en) | 2019-12-25 | 2019-12-25 | Shoe pad and preparation process thereof |
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| CN111019329A true CN111019329A (en) | 2020-04-17 |
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| CN201911352619.8A Pending CN111019329A (en) | 2019-12-25 | 2019-12-25 | Shoe pad and preparation process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113089334A (en) * | 2021-04-07 | 2021-07-09 | 何立梅 | Soft and wear-resistant artificial leather and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113089334A (en) * | 2021-04-07 | 2021-07-09 | 何立梅 | Soft and wear-resistant artificial leather and preparation method thereof |
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