CN111285994A - High-damping wide-damping temperature range shock absorption and energy absorption modifier and preparation method thereof - Google Patents
High-damping wide-damping temperature range shock absorption and energy absorption modifier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-damping wide-damping temperature range shock-absorbing energy-absorbing modifier and a preparation method thereof, belonging to the technical field of high polymer materials, wherein the shock-absorbing energy-absorbing modifier consists of an organic silicon section, a boron-oxygen section, a triazine ring section, a carbamate section and a carbomite section, and in the high polymer structure, various different chain section structures can effectively widen the damping temperature range of the material, and the material can generate a large amount of internal loss to convert a large amount of impact energy when being impacted, the maximum loss factor is 2.82, and the corresponding damping temperature range is-35 ℃ to 128 ℃.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-damping wide-damping temperature range shock absorption and energy absorption modifier and a preparation method thereof.
Background
Since the 21 st century, with the continuous development of polymer materials, the excellent properties of the polymer materials are widely applied to national defense science and technology, high-end manufacturing and people's life, and the polymer materials become one of indispensable materials in modern life and future science and technology development, and the whereabouts of the polymer materials are distributed in every corner of daily life. With the continuous improvement of the quality of life of human beings, the self-protection consciousness is enhanced, and various protective materials are emerging continuously, such as Shear Thickening Fluid (STF) and shear thickening gel which are widely adopted at home and abroad. Shear thickening fluids and gels are non-Newtonian fluids, which exhibit the properties of solids with a rapid increase in apparent viscosity when subjected to high shear from the outside. The composite material can be used as a filler, and can improve the protective performance and comfort of products by being combined with various shell structures or base materials.
However, the shear thickening fluid and the shear thickening gel have the defects of no fixed shape in a normal state, unstable self system, poor compatibility with a matrix material and the like in practical application, so that the application range of the material is greatly reduced. The content of active ingredients in the prepared composite material is difficult to increase, and the composite material is easy to generate unrecoverable deformation; when the shear thickening fluid and the gel are impacted by the outside, the shear thickening fluid and the gel are easy to separate from the base material, so that huge potential safety hazards exist in the practical application of the shear thickening fluid and the gel; and the damping performance thereof is to be further improved.
At present, extreme sports apparel, such as racing suits, cycling suits, locomotive suits, ski suits, and the like; digital product protection, such as cell phones, computers, cameras, etc.; and military products, such as police and military protective equipment, have great demands on protective materials. In order to solve the application problem of high polymer materials in the protection field, research on novel high-performance damping materials and modifiers thereof becomes the key research point of the protection material technology.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-damping wide-damping temperature range shock absorption and energy absorption modifier and a preparation method thereof, the prepared shock absorption and energy absorption modifier can effectively play a role in protection, the maximum loss factor is 2.82, and the corresponding damping temperature range is-35-128 ℃.
In order to achieve the aim of the invention, the invention adopts the specific scheme that:
a high-damping wide-damping temperature range shock absorption energy-absorbing modifier is characterized in that: the shock absorption and energy absorption modifier consists of an organic silicon section, a boron-oxygen section, a triazine ring section, a carbamate section and a carbomite section, the maximum loss factor is 2.82, and the corresponding damping temperature range is-35-128 ℃.
A preparation method of a high-damping wide-damping temperature range shock absorption and energy absorption modifier comprises the following steps:
(1) weighing 100 parts by weight of water, adding 10-20 parts by weight of organic boride and 1-3 parts by weight of organic acid, stirring, and dissolving at 85-95 ℃ for 5-10 min to obtain an organic boride mixed solution;
(2) weighing 100 parts by weight of hydroxyl silicone oil, adding 10-15 parts by weight of the organic boride mixed solution prepared in the step (1), stirring, and reacting at 105-120 ℃ for 30-50 min to obtain a borosiloxane prepolymer;
(3) weighing 100 parts by weight of the borosiloxane prepolymer prepared in the step (2), adding 5-10 parts by weight of melamine and 1-3 parts by weight of filler, stirring, and reacting at 130-140 ℃ for 0.5-1 h; adding 8-12 parts by weight of isocyanate, stirring, and reacting at 155-170 ℃ for 1-2 hours; and after the reaction is finished, cooling to room temperature to obtain the shock absorption and energy absorption modifier with high damping and wide damping temperature range.
As an improvement, the organic boride in the step (1) adopts one or a mixture of boric acid, phenylboronic acid and borate.
As an improvement, the organic acid in the step (1) adopts one or a mixture of more of citric acid, stearic acid and lauric acid.
As an improvement, the hydroxyl content of the hydroxyl silicone oil in the step (2) is 2% -5%, and the viscosity (25 ℃) is 30-100 cp.
As an improvement, the filler in the step (3) is one or a mixture of mica, talcum powder and titanium dioxide.
As an improvement, the isocyanate in the step (3) is one or a mixture of several of diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
The invention has the beneficial effects that:
the modifier with high damping and wide damping temperature range consists of an organic silicon section, a boron-oxygen section, a triazine ring section, a carbamate section and a carbomite section. In the macromolecular structure, various different chain segment structures can effectively widen the damping temperature range of the material, and the material can generate a large amount of internal loss to convert a large amount of impact energy when being impacted, the maximum loss factor is 2.82, and the corresponding damping temperature range is-35-128 ℃.
In the molecular structure of the modifier, an organic silicon segment is used as a main chain to provide good flexibility for a macromolecule, and a boron-oxygen segment, a triazine ring segment, a carbamate segment and a carbodiimide segment are used as a part of the main chain, so that the originally regular molecular structure is discontinuously divided, various chain segments with different glass transition temperatures are formed, and the whole damping temperature range of the modifier is widened.
When the modifier material is impacted, different chain segment structures in the molecular structure of the modifier material have different glass transition temperatures, so that different relaxation times are achieved, and a large amount of internal loss is generated to convert impact energy into heat energy to be dissipated; in addition, hydroxyl, amino and other polar groups in the molecular structure can form abundant hydrogen bond structures, and when the molecular structure is impacted, the hydrogen bond is damaged, so that a large amount of energy is dissipated.
In addition, hydroxyl and polar groups which are not completely reacted in the modifier can be effectively combined with polyurethane, TPE, butyl rubber, nitrile rubber and the like, the modifier is not easy to separate from a base material, and the prepared composite material has good damping performance.
Detailed Description
The present invention is further described below by way of specific examples, but the present invention is not limited to only the following examples. Variations, combinations, or substitutions of the invention, which are within the scope of the invention or the spirit, scope of the invention, will be apparent to those of skill in the art and are within the scope of the invention.
Example 1
A preparation method of a high-damping wide-damping temperature range shock absorption and energy absorption modifier comprises the following steps:
(1) weighing 100g of water, adding 5g of boric acid, 5g of phenylboronic acid and 1g of stearic acid, stirring, and dissolving at 85 ℃ for 5min to obtain an organic boride mixed solution;
(2) weighing 100g of hydroxyl silicone oil with 5% of hydroxyl content and 100cp of viscosity, adding 12g of the organic boride mixed solution prepared in the step (1), stirring, and reacting at 110 ℃ for 30min to obtain a borosiloxane prepolymer;
(3) weighing 100g of the borosiloxane prepolymer prepared in the step (2), adding 5g of melamine, 1g of mica and 2g of talcum powder, stirring, and reacting at 130 ℃ for 40 min; then 8g of diphenylmethane diisocyanate is added, stirred and reacted for 1h at 160 ℃; and after the reaction is finished, cooling to room temperature to obtain the shock absorption and energy absorption modifier with high damping and wide damping temperature range.
The prepared damping energy-absorbing modifier with high damping and wide damping temperature range has the maximum loss factor of 2.45 and the damping temperature range of-37-103 ℃.
Mixing a catalyst, a foaming agent, a foam stabilizer and polyether polyol to prepare a material A; crushing the prepared damping and energy-absorbing modifier, and mixing the crushed and dried modifier with isocyanate to prepare a material B; mixing the material A and the material B, stirring uniformly, pouring the mixture into a mold, foaming, taking out and curing, and then preparing a standard sample strip, wherein the maximum loss factor is 1.72, and the damping temperature range is-31-68 ℃.
Example two
A preparation method of a high-damping wide-damping temperature range shock absorption and energy absorption modifier comprises the following steps:
(1) weighing 100g of water, adding 6g of boric acid, 12g of boric acid ester and 2.1g of citric acid, stirring, and dissolving at 90 ℃ for 10min to obtain an organic boride mixed solution;
(2) weighing 100g of hydroxyl silicone oil with the hydroxyl content of 3% and the viscosity of 50cp, adding 10g of the organic boride mixed solution prepared in the step (1), stirring, and reacting at 120 ℃ for 35min to obtain a borosiloxane prepolymer;
(3) weighing 100g of the borosiloxane prepolymer prepared in the step (2), adding 8.5g of melamine and 2.4g of mica, stirring, and reacting at 140 ℃ for 0.5 h; then adding 3.5g of diphenylmethane diisocyanate and 7.5g of 1, 6-hexamethylene diisocyanate, stirring, and reacting for 2 hours at 155 ℃; and after the reaction is finished, cooling to room temperature to obtain the shock absorption and energy absorption modifier with high damping and wide damping temperature range.
The prepared damping energy-absorbing modifier with high damping and wide damping temperature range has the maximum loss factor of 2.82 and the corresponding damping temperature range of-35-128 ℃.
Mixing butyl rubber, nitrile rubber, filler, compounding agent and the like with the high-damping and wide-damping temperature range shock absorption modifier by using an open mill, thinly taking out a sheet, placing the sheet, vulcanizing the sheet by using a flat vulcanizing machine, and preparing a standard sample strip, wherein the maximum loss factor is 1.96, and the damping temperature range is-32 ℃ to 69 ℃.
EXAMPLE III
A preparation method of a high-damping wide-damping temperature range shock absorption and energy absorption modifier comprises the following steps:
(1) weighing 100g of water, adding 20g of phenylboronic acid, 1.5g of stearic acid and 1.5g of lauric acid, stirring, and dissolving at 95 ℃ for 10min to obtain an organic boride mixed solution;
(2) weighing 100g of hydroxyl silicone oil with the hydroxyl content of 2% and the viscosity of 30cp, adding 15g of the organic boride mixed solution prepared in the step (1), stirring, and reacting at 105 ℃ for 50min to obtain a borosiloxane prepolymer;
(3) weighing 100g of the borosiloxane prepolymer prepared in the step (2), adding 10g of melamine and 1g of titanium dioxide, stirring, and reacting at 135 ℃ for 1 h; then 8g of diphenylmethane diisocyanate and 4g of isophorone diisocyanate are added, stirred and reacted for 1.5h at 170 ℃; and after the reaction is finished, cooling to room temperature to obtain the shock absorption and energy absorption modifier with high damping and wide damping temperature range.
The prepared damping energy-absorbing modifier with high damping and wide damping temperature range has the maximum loss factor of 2.61 and the damping temperature range of-33-142 ℃.
Crushing the prepared high-damping and wide-damping temperature range shock absorption and energy absorption modifier, mixing the crushed and dried modifier with the dried TPE and the antioxidant by using a high-speed mixer, extruding by using a double-screw extruder, granulating, and then performing injection molding to obtain a standard sample strip, wherein the maximum loss factor is 1.85, and the damping temperature range is-48-80 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A high-damping wide-damping temperature range shock absorption energy-absorbing modifier is characterized in that: the shock absorption and energy absorption modifier consists of an organic silicon section, a boron-oxygen section, a triazine ring section, a carbamate section and a carbomite section, the maximum loss factor is 2.82, and the corresponding damping temperature range is-35-128 ℃.
2. The preparation method of the high-damping wide-damping temperature range shock absorption and energy absorption modifier according to claim 1, characterized in that: the preparation method comprises the following steps:
(1) weighing 100 parts by weight of water, adding 10-20 parts by weight of organic boride and 1-3 parts by weight of organic acid, stirring, and dissolving at 85-95 ℃ for 5-10 min to obtain an organic boride mixed solution;
(2) weighing 100 parts by weight of hydroxyl silicone oil, adding 10-15 parts by weight of the organic boride mixed solution prepared in the step (1), stirring, and reacting at 105-120 ℃ for 30-50 min to obtain a borosiloxane prepolymer;
(3) weighing 100 parts by weight of the borosiloxane prepolymer prepared in the step (2), adding 5-10 parts by weight of melamine and 1-3 parts by weight of filler, stirring, and reacting at 130-140 ℃ for 0.5-1 h; adding 8-12 parts by weight of isocyanate, stirring, and reacting at 155-170 ℃ for 1-2 hours; and after the reaction is finished, cooling to room temperature to obtain the shock absorption and energy absorption modifier with high damping and wide damping temperature range.
3. The preparation method of the high-damping wide-damping temperature range shock absorption and energy absorption modifier according to claim 2, characterized in that: the organic boride in the step (1) is one or a mixture of boric acid, phenylboronic acid and borate.
4. The preparation method of the high-damping wide-damping temperature range shock absorption and energy absorption modifier according to claim 2, characterized in that: the organic acid in the step (1) is one or a mixture of more of citric acid, stearic acid and lauric acid.
5. The preparation method of the high-damping wide-damping temperature range shock absorption and energy absorption modifier according to claim 2, characterized in that: the hydroxyl content of the hydroxyl silicone oil in the step (2) is 2% -5%, and the viscosity (25 ℃) is 30-100 cp.
6. The preparation method of the high-damping wide-damping temperature range shock absorption and energy absorption modifier according to claim 2, characterized in that: the filler in the step (3) is one or a mixture of mica, talcum powder and titanium dioxide.
7. The preparation method of the high-damping wide-damping temperature range shock absorption and energy absorption modifier according to claim 2, characterized in that: the isocyanate in the step (3) is one or a mixture of more of diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117285690A (en) * | 2023-09-15 | 2023-12-26 | 苏州易昇光学材料股份有限公司 | Flexible optical buffer material and preparation method and application thereof |
| CN117285690B (en) * | 2023-09-15 | 2024-05-10 | 苏州易昇光学材料股份有限公司 | Flexible optical buffer material and preparation method and application thereof |
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