CN114015227A - Fast-curing slow-resilience acrylic foam and preparation method and application thereof - Google Patents
Fast-curing slow-resilience acrylic foam and preparation method and application thereof Download PDFInfo
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- CN114015227A CN114015227A CN202111579639.6A CN202111579639A CN114015227A CN 114015227 A CN114015227 A CN 114015227A CN 202111579639 A CN202111579639 A CN 202111579639A CN 114015227 A CN114015227 A CN 114015227A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/107—Nitroso compounds
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention provides a fast-curing slow-resilience acrylic foam and a preparation method and application thereof, wherein the fast-curing slow-resilience acrylic foam comprises the following raw materials in parts by weight: 100 parts of acrylic acid polymer; 1-10 parts of isocyanate; 0.3-15 parts of a foaming agent; 0.5-6 parts of a chain extender; 0.03-1 part of delayed catalyst. The acrylic acid foam has a quick curing effect and an excellent slow rebound effect, effectively improves the buffering and sound insulation performance of the foam, and is suitable for being used as a buffering material to be applied to electronic equipment such as sealing and buffering.
Description
Technical Field
The invention belongs to the technical field of foam materials, and relates to fast-curing slow-resilience acrylic foam as well as a preparation method and application thereof.
Background
The slow rebound foam is called low rebound sponge and zero pressure-sensitive foam. The slow rebound foam is a foam material with viscoelasticity, when the foam is deformed under the action of an external force, the strain lags behind the change of stress, so that when the foam is subjected to the external force, the foam does not recover immediately, but slowly recovers to the original shape after 5-40 seconds, and the slow rebound foam has a memory characteristic and is also called as memory foam. The slow rebound foam can conform to the shape of a bearing object due to the rebound resilience, the specific cell structure and the porosity of the slow rebound foam, so that the contact area is maximized, the stress gradient is minimized, the stress concentration point can be relieved, the force dispersion is achieved, the energy absorption is higher, the buffering performance is better, the processing performance is better, the slow rebound foam is frequently used as a buffering material, a sound absorption material, a non-slip material and the like, and the slow rebound foam has the characteristic of impact force absorption and is widely applied in life at present. Is widely applied to the fields of thousands of electrons, electric appliances, digital codes, automobiles, communication and the like.
CN112680139A discloses an acrylic foaming shock attenuation bubble is cotton, acrylic foaming shock attenuation bubble is cotton to be applied to on the OLED module, including from type rete and acrylic bubble cotton layer, from type rete and acrylic bubble cotton layer each other the coincide together, acrylic bubble cotton layer is dried by the cotton coating liquid coating of acrylic acid bubble and is formed, the cotton coating liquid of acrylic acid bubble adopts following component to make: acrylic polymer, isocyanate, foaming microspheres, inorganic filler, dispersant, inorganic pigment and organic solvent. The acrylic foam adhesive tape prepared by the invention can absorb impact force, has excellent impact absorption performance, can be widely used around liquid crystal as a buffer material by utilizing the characteristic, can not cause water decomposition due to excessive humidity, and has excellent durability. However, the acrylic foaming damping foam has the advantages of low curing speed, high density and low resilience to be further improved.
Therefore, in the field, development of a fast curing slow rebound acrylic foam is expected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a fast-curing slow-rebound acrylic foam and a preparation method and application thereof. The acrylic acid foam has a quick curing effect and an excellent slow rebound effect, effectively improves the buffering and sound insulation performance of the foam, can effectively absorb impact kinetic energy by utilizing the characteristic, and is very suitable to be used as a buffering material to be applied to electronic equipment such as sealing and buffering.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to the first aspect, the invention provides a fast-curing slow-resilience acrylic foam, which comprises the following raw materials in parts by weight:
in the present invention, the acrylic polymer having high elasticity is used as the host resin, and the content of primary hydroxyl groups in the acrylic polymer is high, so that the polymer has high reactivity and provides a soft segment. The addition of the foaming agent enables a plurality of foam cell structures which are different in size and are uniformly distributed to be formed in the prepared acrylic foam, and the foam cells absorb impact kinetic energy, so that the acrylic foam has an excellent buffering effect and small compression residual deformation. The addition of the delayed catalyst ensures that the material has longer operation time at normal temperature without influencing the later curing of the product, and when the material reaches the excitation temperature, the delayed catalyst and isocyanate (as a curing agent) have synergistic action so as to quickly finish the gel and curing reaction.
In the invention, the isocyanate can be used in 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts in the raw materials for preparing the fast-curing slow-resilience acrylic foam.
In the invention, in the raw materials for preparing the fast curing slow rebound acrylic foam, the amount of the foaming agent can be 0.3 part, 0.5 part, 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 13 parts or 15 parts, etc.
In the invention, in the raw materials for preparing the fast curing slow rebound acrylic foam, the amount of the chain extender can be 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts or 6 parts.
In the invention, in the raw materials for preparing the fast curing slow rebound acrylic foam, the amount of the delay catalyst can be 0.03 part, 0.05 part, 0.08 part, 0.1 part, 0.15 part, 0.2 part, 0.3 part, 0.5 part, 0.6 part, 0.8 part or 1 part and the like.
Preferably, the acrylic polymer has a number average molecular weight of 3000-.
Preferably, the hydroxyl value of the acrylic polymer is 50 to 150mgKOH/g, such as 50mgKOH/g, 60mgKOH/g, 70mgKOH/g, 80mgKOH/g, 90mgKOH/g, 100mgKOH/g, 110mgKOH/g, 120mgKOH/g, 130mgKOH/g, 140mgKOH/g, 150mgKOH/g, and the like.
Preferably, the acrylic polymer has a solids content of 30-80%, such as 30%, 40%, 50%, 60%, 70%, or 80%, and the like.
Preferably, the acrylic polymer comprises any one of polyester resin, polyurethane resin, epoxy resin, silicone resin, natural rubber blend modified acrylic polymer or natural rubber graft modified acrylic polymer or a combination of at least two thereof.
Preferably, the isocyanate includes any one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), or Lysine Diisocyanate (LDI), or a combination of at least two thereof.
In a preferred embodiment of the present invention, the isocyanate includes any one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, or hexamethylene diisocyanate, or a combination of at least two of them. These isocyanates are selected to have a better curing effect than the other isocyanates.
Preferably, the blowing agent comprises an organic chemical blowing agent or an inorganic chemical blowing agent. The chemical foaming agent is a compound which is decomposed by heating to release gases such as carbon dioxide and nitrogen and form fine pores in a polymer composition, and generally means a thermal decomposition type chemical foaming agent having a powdery characteristic, which can be uniformly dispersed in plastics and rubbers, does not generate gas at a low temperature, and rapidly decomposes at a processing temperature to generate a large amount of gas, thereby foaming it.
Preferably, the organic chemical foaming agent comprises any one of azo compounds, sulfonyl hydrazine compounds, nitroso compounds, triazole compounds or azide compounds or a combination of at least two of the compounds.
Preferably, the organic chemical blowing agent comprises any one of azobisisobutyronitrile, p-toluenesulfonyl hydrazide, dinitrosopentamethylenetetramine, or p-toluenesulfonyl azide, or a combination of at least two thereof.
Preferably, the inorganic chemical blowing agent comprises any one of sodium bicarbonate, ammonium carbonate, ammonium hydrogen nitrate or sodium borohydride, or a combination of at least two thereof.
Preferably, the chain extender includes any one of 1, 4-Butanediol (BDO), 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), sorbitol, Diethylaminoethanol (DEAE), 3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), formaldehyde-modified MOCA, ethylenediamine (DA), or N, N-dihydroxy (diisopropyl) aniline (HPA), or a combination of at least two thereof. The chain extender is a substance which can react with a functional group on a linear polymer chain to expand a molecular chain and increase a molecular weight.
Preferably, the retardation catalyst comprises any one of or a combination of at least two of (acetylacetonato) dibutyltin dilaurate, (acetylacetonato) triethylenediamine, (acetylacetonato) zinc octoate, or (acetylacetonato) ethanolamine. Compared with the conventional catalyst, the delayed catalyst has the advantages that the delayed catalyst enables the material to have longer operation time at normal temperature without influencing the later-period curing of the product, the material starts to play a role of catalysis when reaching the excitation temperature, can be geometrically increased instantly, and the gel and curing reaction is rapidly completed, so that the mixing of the raw materials can be realized, and the longer operation time is realized.
In a second aspect, the present invention provides a method for preparing a fast curing slow rebound acrylic foam according to the first aspect, the method comprising the following steps:
(1) mixing the acrylic polymer, the delayed catalyst, the chain extender, the foaming agent and the organic solvent according to the formula ratio, then adding isocyanate, and dispersing and stirring to obtain a mixed solution;
(2) and coating the mixed solution on a base material, and foaming and forming to obtain the rapidly-cured slow-resilience acrylic foam.
The preparation method is simple and easy to operate.
Preferably, the organic solvent includes any one of an ester organic solvent, a ketone organic solvent, an ether organic solvent, an alcohol organic solvent, an aromatic hydrocarbon organic solvent, an aliphatic organic solvent, or dimethyl sulfoxide, and is preferably an ester organic solvent or a ketone organic solvent.
Preferably, the ester organic solvent includes any one of methyl acetate, ethyl acetate, propyl acetate or butyl acetate or a combination of at least two thereof.
Preferably, the ketone organic solvent includes any one of acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or a combination of at least two thereof.
Preferably, the ether organic solvent includes any one of tetrahydrofuran, tetrahydropyran, or dioxane, or a combination of at least two thereof.
Preferably, the alcoholic organic solvent includes any one of methanol, ethanol, t-butanol, isopropanol or ethylene glycol or a combination of at least two thereof.
Preferably, the aromatic hydrocarbon organic solvent includes any one of benzene, toluene, xylene, naphthalene, or naphtha, or a combination of at least two thereof.
Preferably, the aliphatic hydrocarbon organic solvent comprises any one of hexane, cyclohexane, octane, nonane, decane, undecane, dodecane or mineral essential oil or a combination of at least two thereof.
Preferably, the organic solvent is added in an amount of 20 to 60 parts, for example, 20 parts, 30 parts, 40 parts, 50 parts or 60 parts, etc., based on 100 parts by weight of the acrylic polymer.
Preferably, the base material comprises any one of a monolayer type film, a composite polyester type film, a coating type polyester film or a high molecular co-extrusion resin film.
Preferably, the substrate includes any one of polyethylene terephthalate, polyimide, polyamide, an aluminum-plated film, polypropylene, or polytetrafluoroethylene. In the present invention, the substrate serves as a carrier for the preparation of the fast curing slow rebound acrylic foam.
Preferably, the mixing of step (1) is high speed mixing.
Preferably, the mixing time in step (1) is 30-60 min, such as 30min, 40min, 50min or 60 min.
Preferably, the dispersion stirring of step (1) is high-speed dispersion stirring.
Preferably, the time for dispersing and stirring in the step (1) is 30-60 min, such as 30min, 40min, 50min or 60 min.
Preferably, the foaming molding in the step (2) is performed in an oven, and the temperature of the oven is set as follows: the temperature of the first section of oven is 60-70 ℃ (60 ℃, 65 ℃ or 70 ℃ and the like), the temperature of the second section of oven is 60-70 ℃ (60 ℃, 65 ℃ or 70 ℃ and the like), the temperature of the third section of oven is 70-80 ℃ (70 ℃, 75 ℃ or 80 ℃ and the like), the temperature of the fourth section of oven is 80-90 ℃ (80 ℃, 85 ℃ or 90 ℃ and the like), the temperature of the fifth section of oven is 80-90 ℃ (80 ℃, 85 ℃ or 90 ℃ and the like), the temperature of the sixth section of oven is 130-140 ℃ (130 ℃, 135 ℃ or 140 ℃ and the temperature of the seventh section of oven is 130-140 ℃ (130 ℃, 135 ℃ or 140 ℃ and the like).
Preferably, the foaming time in step (2) is 1-3min, such as 1min, 2min or 3 min.
Preferably, the thickness of the fast-curing slow rebound acrylic foam in the step (2) is 50-400 μm, such as 50 μm, 100 μm, 200 μm, 300 μm or 400 μm.
In a third aspect, the invention provides the use of the fast curing slow rebound acrylic foam of the first aspect in a cushioning material.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) in the present invention, the acrylic polymer having high elasticity is used as the host resin, and the content of primary hydroxyl groups in the acrylic polymer is high, so that the polymer has high reactivity and provides a soft segment. The addition of the foaming agent enables a plurality of foam cell structures with different sizes and uniform distribution to be formed in the prepared acrylic foam, and the foam cells absorb impact kinetic energy, so that the acrylic foam has excellent buffering effect and smaller compression residual deformation (50% compression permanent deformation is less than or equal to 5%).
(2) In the invention, the addition of the delayed catalyst ensures that the material has longer operation time at normal temperature without influencing the later curing of the product, and when the material reaches the excitation temperature, the delayed catalyst and the isocyanate have synergistic action to quickly finish the gel and curing reaction.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a fast-curing slow-resilience acrylic foam, and the preparation raw materials of the fast-curing slow-resilience acrylic foam comprise the following components in parts by weight:
wherein, the acrylic polymer (with the trade name of YZ-H305 in the Jack chemical industry) has the number average molecular weight of 4000, the hydroxyl value of 54mgKOH/g and the solid content of 40 percent; the isocyanate is toluene diisocyanate; the foaming agent is azodiisobutyronitrile; the chain extender is 1, 4-butanediol; the delayed action catalyst was dibutyltin (acetylacetonate) dilaurate.
The preparation method comprises the following steps:
(1) mixing, dispersing and stirring acrylic polymer, a delayed catalyst, a chain extender, a foaming agent and an organic solvent with a formula ratio at a high speed for 40min, then adding isocyanate, and mixing, dispersing and stirring at a high speed for 30min to obtain a mixed solution;
(2) and coating the mixed solution on a substrate, putting the substrate into an oven for heating, and carrying out foaming molding to obtain the rapidly-cured slow-resilience acrylic foam.
Wherein the organic solvent is ethyl acetate; the adding amount of the organic solvent is 40 parts by weight based on 100 parts by weight of the acrylic polymer; the substrate is polyethylene terephthalate.
The oven temperature was set as follows: the temperature of the first section of drying oven is 65 ℃, the temperature of the second section of drying oven is 65 ℃, the temperature of the third section of drying oven is 75 ℃, the temperature of the fourth section of drying oven is 85 ℃, the temperature of the fifth section of drying oven is 85 ℃, the temperature of the sixth section of drying oven is 135 ℃, and the temperature of the seventh section of drying oven is 135 ℃; the foaming time was 3 min.
Example 2
The embodiment provides a fast-curing slow-resilience acrylic foam, and the preparation raw materials of the fast-curing slow-resilience acrylic foam comprise the following components in parts by weight:
wherein, the acrylic polymer (with the trade name of YZ-H706 in Jack chemical industry) has the number average molecular weight of 5000, the hydroxyl value of 70mgKOH/g and the solid content of 60 percent; the isocyanate is isophorone diisocyanate; the foaming agent is p-toluenesulfonyl hydrazide; the chain extender is 1, 6-hexanediol; the delayed catalyst is (acetylacetone) triethylenediamine.
The preparation method comprises the following steps:
(1) mixing, dispersing and stirring acrylic polymer, a delayed catalyst, a chain extender, a foaming agent and an organic solvent in a formula ratio at a high speed for 30min, then adding isocyanate, and mixing, dispersing and stirring at a high speed for 60min to obtain a mixed solution;
(2) and coating the mixed solution on a substrate, putting the substrate into an oven for heating, and carrying out foaming molding to obtain the rapidly-cured slow-resilience acrylic foam.
Wherein the organic solvent is butyl acetate; the adding amount of the organic solvent is 60 parts by weight based on 100 parts by weight of the acrylic polymer; the substrate is polyethylene terephthalate.
The oven temperature settings were the same as in example 1.
Example 3
The embodiment provides a fast-curing slow-resilience acrylic foam, and the preparation raw materials of the fast-curing slow-resilience acrylic foam comprise the following components in parts by weight:
wherein, the number average molecular weight of the acrylic polymer (the trade name is YZ-H638 in Jack chemical industry) is 8000, the hydroxyl value is 75mgKOH/g, and the solid content is 60 percent; the isocyanate is diphenylmethane diisocyanate; the foaming agent is dinitrosopentamethylenetetramine; the chain extender is glycerol; the delayed catalyst is zinc (acetylacetonate) octoate.
The preparation method comprises the following steps:
(1) mixing, dispersing and stirring acrylic polymer, a delayed catalyst, a chain extender, a foaming agent and an organic solvent in a formula ratio for 50min at a high speed, then adding isocyanate, and mixing, dispersing and stirring for 50min at a high speed to obtain a mixed solution;
(2) and coating the mixed solution on a substrate, putting the substrate into an oven for heating, and carrying out foaming molding to obtain the rapidly-cured slow-resilience acrylic foam.
Wherein the organic solvent is methyl ethyl ketone; the adding amount of the organic solvent is 40 parts by weight based on 100 parts by weight of the acrylic polymer; the substrate is polyethylene terephthalate.
The oven temperature settings were the same as in example 1.
Example 4
The embodiment provides a fast-curing slow-resilience acrylic foam, and the preparation raw materials of the fast-curing slow-resilience acrylic foam comprise the following components in parts by weight:
wherein, the acrylic polymer (the trade name is Z-H880 of Jack chemical industry) has the number average molecular weight of 10000, the hydroxyl value of 100mgKOH/g and the solid content of 80 percent; the isocyanate is hexamethylene diisocyanate; the foaming agent is p-toluenesulfonyl azide; the chain extender is ethylenediamine; the delayed catalyst is (acetylacetone) ethanolamine.
The preparation method comprises the following steps:
(1) mixing, dispersing and stirring acrylic polymer, a delayed catalyst, a chain extender, a foaming agent and an organic solvent with the formula ratio at a high speed for 60min, then adding isocyanate, and mixing, dispersing and stirring at a high speed for 40min to obtain a mixed solution;
(2) and coating the mixed solution on a substrate, putting the substrate into an oven for heating, and carrying out foaming molding to obtain the rapidly-cured slow-resilience acrylic foam.
Wherein the organic solvent is toluene; the adding amount of the organic solvent is 55 parts by weight based on 100 parts by weight of the acrylic polymer; the substrate is polyethylene terephthalate.
The oven temperature settings were the same as in example 1.
Example 5
This example differs from example 1 only in that the blowing agent azobisisobutyronitrile was replaced with the same amount of expanded microspheres in CN112680139A, and the other conditions were the same as in example 1.
Example 6
This example differs from example 1 only in that toluene diisocyanate was replaced with the same amount of lysine diisocyanate and the other conditions were the same as in example 1.
Example 7
This example differs from example 1 only in that the delayed catalyst dibutyltin dilaurate (acetylacetonate) was replaced by the same amount of dibutyltin dilaurate, and the other conditions were the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that the blowing agent was not included in the starting materials for preparation, and the other conditions were the same as in example 1.
Comparative example 2
This comparative example is different from example 2 only in that the blowing agent is 25 parts by weight and the other conditions are the same as example 2.
Comparative example 3
This comparative example differs from example 3 only in that diphenylmethane diisocyanate was not included in the starting materials and the other conditions were the same as in example 3.
Comparative example 4
This comparative example differs from example 4 only in that no chain extender was included in the starting materials for preparation, and the other conditions were the same as in example 4.
Comparative example 5
This comparative example differs from example 3 only in that the preparation starting material does not include the delayed catalyst (acetylacetone) zinc octoate, and the other conditions are the same as in example 3.
The acrylic foam provided in examples 1 to 7 and comparative examples 1 to 5 were subjected to a performance test by the following method:
1. thickness measurement
(1) When sampling from the film roll, at least the outermost three circles of the film are removed;
(2) placing the well-taken sample in a standard test environment for at least 3 h;
(3) and placing the sample between the upper head plane and the lower head plane of the measuring head of the thickness gauge, enabling the foam face to face upwards, slowly descending the upper measuring head during the test, and finally covering the surface of the foam face. Within 1 second after the upper measuring head is lowered, recording the reading of a dial gauge of the thickness gauge, and indicating the reading in mm to be accurate to 0.001 mm;
(4) measuring 9 points on each single sheet, recording data and calculating an average value; wherein the distance between every 2 points is not less than 50 mm.
2. Density test
(1) When sampling from the film roll, at least the outermost three circles of the film are removed;
(2) placing the well-taken sample in a standard test environment for at least 3 h;
(3) cutting the sample into 10cm by 10cm samples at room temperature, testing the weight of the monomer foam to be m, and recording the thickness testing method as the testing condition as h;
(4) density calculation formula: ρ is m/h 100.
3. Compression strength test
(1) Taking a roll-shaped or sheet-shaped sample, cutting the product into strips with the size of 50mm multiplied by 200mm, and standing for more than 2h under the test condition;
(2) superposing the samples layer by layer to prepare samples with the size of 25mm by 10mm, and standing for 24 hours at constant temperature in a laboratory after the completion;
(3) testing the sample by using a universal mechanical press, wherein the compression speed is 5mm/min, and performing compression test on the sample;
(4) the compression strength data values corresponding to 25% and 50% compression ratios, respectively, are taken.
4. Compression set test: the test was carried out according to the method of GB/T6669-2008.
5. Falling ball impact test
(1) Taking a roll-shaped or sheet-shaped sample, cutting the product into strips with the size of 100mm multiplied by 100mm, and standing for more than 2h under the test condition;
(2) mobile phone cover glass, sample specification: 60mm 120mm 0.7mm, adhering acrylic foam material;
(3) the weight of the stainless steel ball is 55g, the diameter of the stainless steel ball is 25mm, the impact test is carried out on the mobile phone glass cover plate attached to the foam at the height of 500mm, and whether a sample is intact is observed.
The results of the performance tests are shown in table 1.
TABLE 1
As can be seen from Table 1, the density of the acrylic foams prepared in examples 1 to 4 of the present invention was 0.3 to 0.5g/cm3The foaming thickness can be adjusted between 100-400 mu m, the high-strength polyurethane foam has good compression strength and rebound resilience, the compression permanent deformation is less than or equal to 5 percent, and the high-strength polyurethane foam has good impact absorption performance and buffering and damping performance and can well protect products. By utilizing the characteristics, the acrylic foam can be used as a buffer material to be applied to the periphery of liquid crystal, and the detection results of the embodiments 1-4 are all in the range of the test requirements, so that the use requirements are met.
The acrylic foam prepared in examples 5 to 7 had a thickness and a density meeting the performance requirements, but had an unsatisfactory compression resistance, failed to rebound after long-term compression, and had a compression strength that was either greater or lower according to examples 5 to 7.
The acrylic acid foam prepared in the comparative example has the performance which is not in line with the requirements, obviously has no buffering performance, leads to the breakage of test glass, has larger compression deformation, can not rebound well, and can not play the roles of slow rebound performance and buffering effect.
The applicant states that the invention is illustrated by the above examples to the fast curing slow rebound acrylic foam of the invention and the preparation method and application thereof, but the invention is not limited by the above examples, that is, the invention is not meant to be implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The fast-curing slow-resilience acrylic foam is characterized in that the fast-curing slow-resilience acrylic foam comprises the following raw materials in parts by weight:
2. the fast curing slow rebound acrylic foam as set forth in claim 1, wherein the acrylic polymer has a number average molecular weight of 3000-;
preferably, the hydroxyl value of the acrylic polymer is 50 to 150 mgKOH/g;
preferably, the acrylic polymer has a solids content of 30-80%;
preferably, the acrylic polymer comprises any one of polyester resin, polyurethane resin, epoxy resin, silicone resin, natural rubber blend modified acrylic polymer or natural rubber graft modified acrylic polymer or a combination of at least two thereof.
3. The fast curing slow rebound acrylic foam according to claim 1 or 2, wherein the isocyanate comprises any one or a combination of at least two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate or lysine diisocyanate;
preferably, the isocyanate comprises any one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate or a combination of at least two thereof.
4. The fast curing slow rebound acrylic foam according to any one of claims 1 to 3, wherein the blowing agent comprises an organic chemical blowing agent or an inorganic chemical blowing agent;
preferably, the organic chemical foaming agent comprises any one or a combination of at least two of azo compounds, sulfonyl hydrazine compounds, nitroso compounds, imidazole compounds or azide compounds;
preferably, the organic chemical blowing agent comprises any one of azodiisobutyronitrile, p-toluenesulfonyl hydrazide, dinitrosopentamethylenetetramine, or p-toluenesulfonyl azide or a combination of at least two thereof;
preferably, the inorganic chemical blowing agent comprises any one of sodium bicarbonate, ammonium carbonate, ammonium hydrogen nitrate or sodium borohydride, or a combination of at least two thereof.
5. The fast curing slow rebound acrylic foam of any one of claims 1 to 4, wherein the chain extender comprises any one of or a combination of at least two of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, formaldehyde-modified 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, ethylenediamine or N, N-dihydroxy (diisopropyl) aniline.
6. The fast curing slow rebound acrylic foam according to any one of claims 1 to 5 wherein the delay catalyst comprises any one or a combination of at least two of dibutyl tin dilaurate (acetylacetonate), triethylenediamine (acetylacetonate), zinc octoate (acetylacetonate), or ethanolamine (acetylacetonate).
7. The preparation method of the fast-curing slow rebound acrylic foam as set forth in any one of claims 1 to 6, wherein the preparation method comprises the steps of:
(1) mixing the acrylic polymer, the delayed catalyst, the chain extender, the foaming agent and the organic solvent according to the formula ratio, then adding isocyanate, and dispersing and stirring to obtain a mixed solution;
(2) and coating the mixed solution on a base material, and foaming and forming to obtain the rapidly-cured slow-resilience acrylic foam.
8. The method according to claim 7, wherein the organic solvent comprises any one of an ester organic solvent, a ketone organic solvent, an ether organic solvent, an alcohol organic solvent, an aromatic hydrocarbon organic solvent, an aliphatic organic solvent, or dimethyl sulfoxide, preferably an ester organic solvent or a ketone organic solvent;
preferably, the ester organic solvent includes any one or a combination of at least two of methyl acetate, ethyl acetate, propyl acetate, or butyl acetate;
preferably, the ketone organic solvent comprises any one or a combination of at least two of acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone;
preferably, the ether organic solvent comprises any one of tetrahydrofuran, tetrahydropyran or dioxane or a combination of at least two of tetrahydrofuran, tetrahydropyran and dioxane;
preferably, the alcoholic organic solvent comprises any one of methanol, ethanol, tert-butanol, isopropanol or ethylene glycol or a combination of at least two thereof;
preferably, the aromatic hydrocarbon organic solvent includes any one or a combination of at least two of benzene, toluene, xylene, naphthalene, or naphtha;
preferably, the aliphatic hydrocarbon organic solvent comprises any one or a combination of at least two of hexane, cyclohexane, octane, nonane, decane, undecane, dodecane or mineral essential oil;
preferably, the adding amount of the organic solvent is 20-60 parts by weight based on 100 parts by weight of the acrylic polymer;
preferably, the base material comprises any one of a single-layer film, a composite polyester film, a coating type polyester film or a high-molecular co-extrusion resin film;
preferably, the substrate includes any one of polyethylene terephthalate, polyimide, polyamide, an aluminum-plated film, polypropylene, or polytetrafluoroethylene.
9. The production method according to claim 7 or 8, wherein the mixing of step (1) is high-speed mixing;
preferably, the mixing time in the step (1) is 30-60 min;
preferably, the dispersion stirring in the step (1) is high-speed dispersion stirring;
preferably, the time for dispersing and stirring in the step (1) is 30-60 min;
preferably, the foaming molding in the step (2) is performed in an oven, and the temperature of the oven is set as follows: the temperature of the first section of drying oven is 60-70 ℃, the temperature of the second section of drying oven is 60-70 ℃, the temperature of the third section of drying oven is 70-80 ℃, the temperature of the fourth section of drying oven is 80-90 ℃, the temperature of the fifth section of drying oven is 80-90 ℃, the temperature of the sixth section of drying oven is 130-140 ℃, and the temperature of the seventh section of drying oven is 130-140 ℃;
preferably, the foaming molding time of the step (2) is 1-3 min;
preferably, the thickness of the fast-curing slow-rebound acrylic foam in the step (2) is 50-400 μm.
10. Use of a fast curing slow rebound acrylic foam according to any one of claims 1 to 6 in a cushioning material.
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