CN107903612A - A kind of antifatigue environment-friendly materials and preparation method thereof - Google Patents
A kind of antifatigue environment-friendly materials and preparation method thereof Download PDFInfo
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- CN107903612A CN107903612A CN201711228336.3A CN201711228336A CN107903612A CN 107903612 A CN107903612 A CN 107903612A CN 201711228336 A CN201711228336 A CN 201711228336A CN 107903612 A CN107903612 A CN 107903612A
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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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of antifatigue environment-friendly materials and preparation method thereof, including following parts by weight raw material to be prepared：25 parts of nanometer basalt fibre, 25 parts of modifying agent, 25 40 parts of polyurethane rubber, 55 75 parts of starch, 0.3 0.8 parts of coupling agent, the polyvinyl alcohol of 35 parts of 5 10 parts of crosslinking agent；The present invention is for composite by the nanometer basalt fibre Jing Guo specific aim modification and starch, and a nanometer basalt fibre is dispersed in starch system, and obtained environment-friendly materials anti-fatigue performance is excellent, is conducive to application of the starch in more areas.
Description
Technical field
The present invention relates to modified material field, and in particular to a kind of antifatigue environment-friendly materials and preparation method thereof.
Background technology
Starch is a kind of natural polymers, and great amount of hydroxy group is contained in its molecule, therefore between starch polymer mutually
Active force is very strong, causes ative starch to be difficult to melt-processed, and be blended with other polymers in processing and other polymers
Compatibility is also poor.But these hydroxyls such as can be esterified, be etherified, being grafted, being crosslinked at the chemical reaction.Utilize these chemical reactions pair
Starch carries out chemical modification, reduces the hydroxyl of starch, changes its original structure, so as to change the corresponding performance of starch, original
Starch becomes thermoplastic starch.Crosslinked starch is using starch as raw material, with phosphorus oxychloride, sodium trimetaphosphate, adipic acid, hexametaphosphate
For crosslinking agent, sodium hydroxide is catalyst, and starch is crosslinked, and the starch after crosslinking its light transmittance reduces, resistance to acid and alkali, resistance to
Mechanical processing, endurance of cutting enhancing, gelling performance improves, but water absorbing capacity weakens.
With the continuous improvement that people require material anti-fatigue performance, the starch without antifatigue modification has been difficult to meet
Demand, thus, antifatigue modification is carried out to starch and is necessitated.It is numerous to the antifatigue modification processing method species of starch now
More, modified effect is also fine, and especially with the appearance and application of nano material, the fatigue resistance of starch increases significant effect,
Starch is set largely to be used in more areas, but there is also deficiency.Although nano material has, antifatigue enhancing effect is good, addition
Measure the advantages of small, but there is also difficulties in dispersion, it is of high cost the defects of.In antifatigue modifying process is carried out, nano material is disperseed
Inequality can influence its antifatigue effect, and obtained modified material fatigue resistance is poor, and the production and application to modified material cause
Adverse effect.
The content of the invention
The defects of it is an object of the invention to overcome existing environmental protection starch material fatigue resistance poor, there is provided a kind of antifatigue
Environment-friendly materials and preparation method thereof；The present invention is answered the nanometer basalt fibre Jing Guo specific aim modification and starch
Close, and a nanometer basalt fibre is dispersed in starch system, obtained environment-friendly materials anti-fatigue performance is excellent, is conducive to
Application of the starch in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of antifatigue environment-friendly materials, including following parts by weight are former
Material is prepared：2-5 parts of nanometer basalt fibre, 2-5 parts of modifying agent, 25-40 parts of polyurethane rubber, 55-75 parts
Starch, 0.3-0.8 parts of coupling agent, 3-5 parts of crosslinking agent, 5-10 parts of polyvinyl alcohol.
A kind of above-mentioned antifatigue environment-friendly materials, can increase resin material fatigue resistance according to nanometer basalt fibre and crosslinking
Basic principle, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve a nanometer basalt fibre
Compatibility between dimension and starch, and make nanometer basalt fibre disperse evenly, to make a nanometer basalt fibre pair in starch
The fatigue resistance humidification of starch is more preferable, also makes modified environment-friendly materials antifatigue by controlling the degree of polymerization of starch
Reach optimum balance relation between property and processability, so that the environment-friendly materials made are in the condition with excellent fatigue resistance
Under, it may have excellent processability, allows it to be applied in more areas.
A kind of above-mentioned antifatigue environment-friendly materials, wherein, a diameter of 1-10nm of nanometer basalt fibre, draw ratio is
2-10 ︰ 1；Nanometer basalt fibre draw ratio is bigger, and dispersiveness is poorer, and nanometer basalt fibre draw ratio is smaller, to starch
Tensile strength humidification is poorer；Preferably, a diameter of 3-5nm of nanometer basalt fibre, draw ratio are 3-6 ︰ 1.
A kind of above-mentioned antifatigue environment-friendly materials, wherein, the modifying agent is acrylic acid hydroxyl ester and dimethyl methyl phosphonate
The mixture of composition；The modifying agent can improve the compatibility of nanometer basalt fibre and starch and in the nanometer Black Warrior
Rock fiber surface forms polar group, beneficial to scattered；Preferably, acrylic acid hydroxyl ester and methylphosphonic acid diformazan in the modifying agent
The ratio between amount of material of ester is 1 ︰ 1.
A kind of above-mentioned antifatigue environment-friendly materials, wherein, the degree of polymerization of polyurethane rubber is bigger, then environment-friendly materials after being crosslinked
Fatigue resistance is poorer, and processability is better, and the polymer of polyurethane rubber is smaller, then the fatigue resistance of environment-friendly materials is got over after being crosslinked
Good, processability is poorer, therefore, selects the rational polyurethane rubber degree of polymerization, is the important hand for balancing fatigue resistance and processability
Section.The degree of polymerization of the polyurethane rubber is 800-1200；Preferably, the degree of polymerization of the polyurethane rubber is 900-
1100；Optimal, the degree of polymerization of the polyurethane rubber is 1000；By preferred, obtained environment-friendly materials had both had excellent
Fatigue resistance, it may have preferable processability, is adapted to the application in more areas.
Wherein, the starch degree of polymerization is 800-1200；Preferably, the degree of polymerization of the starch is 900-1100；Most
Preferably, the degree of polymerization of the starch is 1000；By preferred, obtained environment-friendly materials both have excellent fatigue resistance,
Also there is preferable processability.
A kind of above-mentioned antifatigue environment-friendly materials, wherein, the coupling agent is epoxy silane coupling；Epoxy radicals silicone hydride
The compatibility between nanometer basalt fibre and starch and modifying agent can be increased, improve the performance of environment-friendly materials.
Wherein, the crosslinking agent is ethylene glycol dimethacrylate, which can be by two kinds of different polymerization degrees
Polymer raw materials are suitably crosslinked, and improve the fatigue resistance of environment-friendly materials.
A kind of above-mentioned antifatigue environment-friendly materials, wherein, its raw material further includes dispersant, plasticizer, antistatic additive, dyeing
One or more auxiliary agents in agent, brightener；Above-mentioned auxiliary agent can improve the processability of environment-friendly materials, increase the work such as its feature
With so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of preparation of antifatigue environment-friendly materials
Method, comprises the following steps：
（1）Nanometer basalt fibre is handled with coupling agent；
（2）Nanometer basalt fibre Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nanometer basalt fibre after cladding and starch processing for composite in the electric field after mixing, mixed
Material；
（4）By mixture and polyurethane rubber, crosslinking agent, polyvinyl alcohol it is uniform after in processing for composite, obtain anti-tired
Labor environment-friendly materials.
A kind of preparation method of antifatigue environment-friendly materials, first carries out coupling processing with coupling agent to nanometer basalt fibre,
Increase nanometer basalt fibre and modifying agent, the compatibility of starch；Place is modified to nanometer basalt fibre with modifying agent again
Reason, and form polar group on its surface；Finally make the polarity in nanometer basalt fibre surface and starch chain using external electric field
Group polarizes, powered, by repelling each other between electric charge or attracting principle, while making nanometer basalt fibre dispersed,
Can be bonded with the polar group on starch chain, so that the antifatigue enhancing effect of nanometer basalt fibre obtains farthest
Embody, so as to get modified starch fatigue resistance significantly improve；The preparation method is simple and reliable, is suitable for antifatigue environmentally friendly material
Extensive, the industrialized production of material.
A kind of preparation method of above-mentioned antifatigue environment-friendly materials, wherein, it is preferred that step 1 is carried out during coupling processing
Ultrasonic wave can be used to aid in；Shaken by the high speed of ultrasonic wave, make nanometer basalt fibre dispersiveness more preferable, and to coupling processing
With facilitation.
A kind of preparation method of above-mentioned antifatigue environment-friendly materials, wherein, the electric field energy described in step 3 produces pole to group
Change acts on, and makes group powered, so as to promote the scattered and bonded effect of nanometer basalt fibre, improves the anti-tired of modified starch
Lao Xing.
Preferably, the electric field strength is 0.5-2kv/m；Electric field strength is too small, and polarization effect is weak, to nanometer basalt
The dispersion effect of fiber is poor；Electric field strength is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces orientation and moves
It is dynamic, arrangement and the bonded performance for having an impact, may be decreased environment-friendly materials to strand；Most preferably, the electric-field strength
Spend for 0.8-1.5kv/m.
Wherein, it is preferred that the electric field is the constant parallel electric field of direction of an electric field；The constant parallel electric field of direction of an electric field
Best to the polarization effect of polar group, group intermolecular forces are stablized, the scattered and bonded promotion to nanometer basalt fibre
Action effect is optimal.
Compared with prior art, beneficial effects of the present invention：
1st, environment-friendly materials of the present invention targetedly screen the species of modifying agent, coupling agent and crosslinking agent, make a nanometer basalt fibre
Compatibility between starch is more preferable, and the dispersiveness in starch is more preferable, and nanometer basalt fibre increases the fatigue resistance of starch
Pretend with more preferable.
2nd, environment-friendly materials of the present invention pass through the environment-friendly materials that control the degree of polymerization of starch and polyurethane rubber to make modified
Reach optimum balance relation between fatigue resistance and processability, so as to get environment-friendly materials with excellent fatigue resistance
Under the conditions of, it may have excellent processability.
3rd, the preparation method of environment-friendly materials of the present invention, using the polarization of external electric field, can promote nanometer basalt fibre
Scattered and bonded in starch system, the antifatigue enhancing effect of nanometer basalt fibre is more preferable, obtained environment-friendly materials
Fatigue resistance higher.
4th, the preparation method of environment-friendly materials of the present invention is simple, reliable, is adapted to extensive, the industrialization of antifatigue environment-friendly materials
Production.
Embodiment
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）3 parts of nanometer basalt fibre is handled with 0.5 part of epoxy radicals silicone hydride；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of methylphosphonic acid two
Methyl esters carries out cladding processing；
（3）By starch that the nanometer basalt fibre after cladding and 65 parts of the degree of polymerization are 1000 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, mixture is obtained；
（4）Polyurethane rubber that the mixture that step 3 is obtained and 35 parts of the degree of polymerization are 1000,4 parts of dimethacrylate second
Extruded after diol ester, 8 parts of polyvinyl alcohol are uniform, obtain antifatigue environment-friendly materials.
Embodiment 2
（1）2 parts of nanometer basalt fibre is handled with 0.3 part of epoxy radicals silicone hydride；
（2）By nanometer basalt fibre 1 part of the acrylic acid hydroxyl ester and 1 part of dimethyl methyl phosphonate Jing Guo coupling agent treatment
Carry out cladding processing；
（3）By starch that the nanometer basalt fibre after cladding and 55 parts of the degree of polymerization are 800 after mixing in electric-field strength
Spend in the electric field for 2.0kv/m and extruded, obtain mixture；
（4）Polyurethane rubber that the mixture that step 3 is obtained and 25 parts of the degree of polymerization are 800,3 parts of dimethacrylate second two
Extruded after alcohol ester, 5 parts of polyvinyl alcohol are uniform, obtain antifatigue environment-friendly materials.
Embodiment 3
（1）5 parts of nanometer basalt fibre is handled with 0.6 part of epoxy radicals silicone hydride；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 2.5 parts of acrylic acid hydroxyl ester and 2.5 parts of methylphosphonic acid two
Methyl esters carries out cladding processing；
（3）By starch that the nanometer basalt fibre after cladding and 75 parts of the degree of polymerization are 1200 after mixing in electric-field strength
Spend to be extruded in the constant parallel electric field of the direction of an electric field of 0.5kv/m, obtain mixture；
（4）Polyurethane rubber that the mixture that step 3 is obtained and 40 parts of the degree of polymerization are 1200,5 parts of dimethacrylate second
Extruded after diol ester, 10 parts of polyvinyl alcohol are uniform, obtain antifatigue environment-friendly materials.
Comparative example 1
（1）3 parts of nanometer basalt fibre is handled with 0.5 part of epoxy radicals silicone hydride；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment and 3 parts of dispersant, the starch that 65 parts of the degree of polymerization is 1000
Extruded after mixing in the constant parallel electric field of the direction of an electric field that electric field strength is 1.2kv/m, obtain mixture；
（3）Polyurethane rubber that the mixture that step 2 is obtained and 12 parts of the degree of polymerization are 1000,4 parts of dimethacrylate second
Extruded after diol ester, 8 parts of polyvinyl alcohol are uniform, obtain environment-friendly materials.
Comparative example 2
（1）3 parts of nanometer basalt fibre is handled with 0.5 part of epoxy radicals silicone hydride；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of methylphosphonic acid two
Methyl esters carries out cladding processing；
（3）It is 1000 by starch that the nanometer basalt fibre after cladding and 65 parts of the degree of polymerization are 1000,35 parts of the degree of polymerization
Polyurethane rubber, 4 parts of ethylene glycol dimethacrylate, 8 parts of polyvinyl alcohol it is uniform after extruded, obtain environmental protection
Material.
Comparative example 3
（1）3 parts of nanometer basalt fibre is handled with 0.5 part of epoxy radicals silicone hydride；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of polystyrene and 1.5 parts of methylphosphonic acid diformazan
Ester carries out cladding processing；
（3）By starch that the nanometer basalt fibre after cladding and 65 parts of the degree of polymerization are 1000 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, mixture is obtained；
（4）Polyurethane rubber that the mixture that step 3 is obtained and 35 parts of the degree of polymerization are 1000,4 parts of dimethacrylate second
Extruded after diol ester, 8 parts of polyvinyl alcohol are uniform, obtain environment-friendly materials.
Comparative example 4
（1）3 parts of nanometer basalt fibre is handled with 0.5 part of epoxy radicals silicone hydride；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of methylphosphonic acid two
Methyl esters carries out cladding processing；
（3）By the polyurethane rubber of the nanometer basalt fibre after cladding and 35 parts of the degree of polymerization for 1000,4 parts of dimethyl allenes
The starch that sour glycol ester, 8 parts of polyvinyl alcohol, 65 parts of the degree of polymerization are 1000 is after mixing 1.2kv/ in electric field strength
Extruded in the constant parallel electric field of the direction of an electric field of m, obtain environment-friendly materials.
Comparative example 5
（1）3 parts of nanometer basalt fibre is handled with 0.5 part of epoxy radicals silicone hydride；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of methylphosphonic acid two
Methyl esters carries out cladding processing；
（3）By starch that the nanometer basalt fibre after cladding and 65 parts of the degree of polymerization are 1300 after mixing in electric field strength
To be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, mixture is obtained；
（4）Polyurethane rubber that the mixture that step 3 is obtained and 35 parts of the degree of polymerization are 600,8 parts of polyvinyl alcohol, 4 part two
Methacrylic acid glycol ester is extruded after mixing, obtains environment-friendly materials.
By the environment-friendly materials in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data are as follows：
| Performance | Fatigue resistance | Processability |
| Embodiment 1 | ++++++ | ++++ |
| Embodiment 2 | ++++++ | ++++ |
| Embodiment 3 | ++++++ | ++++ |
| Comparative example 1 | ++++ | ++++ |
| Comparative example 2 | ++++ | ++++ |
| Comparative example 3 | +++++ | ++++ |
| Comparative example 4 | +++++ | ++++ |
| Comparative example 5 | +++++ | ++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the antifatigue environment-friendly materials of the invention being prepared in embodiment 1-3, nanometer
Basalt fibre is uniformly dispersed, and good with the compatibility of starch, environment-friendly materials fatigue resistance is good, and processability is good；And in comparative example 1,
Modifying agent is not used processing is modified to nanometer basalt fibre, although adding dispersant, nanometer basalt fibre point
Scattered effect is poor, and the poor compatibility with starch, the fatigue resistance of environment-friendly materials significantly reduces；Do not carried out in the electric field in comparative example 2
Combined processing, nanometer basalt fibre dispersion effect is poor, and the fatigue resistance of environment-friendly materials significantly reduces；Modifying agent in comparative example 3
It is not the application defined, nanometer basalt fibre dispersion effect is poor, and the fatigue resistance of environment-friendly materials significantly reduces；Comparative example
Cross-linking reaction equally carries out in the electric field in 4, and electric field has a negative impact cross-linking reaction, so as to get BS resin materials it is anti-
Fatigability reduces；The starch and the polyurethane rubber degree of polymerization used in comparative example 5 is too small, and compound rear fatigue resistance is preferable, but adds
Work significantly reduces, and is unfavorable for the application of environment-friendly materials.
Claims (10)
1. a kind of antifatigue environment-friendly materials, it is characterised in that be prepared including following parts by weight raw material：2-5 parts of nanometer
Basalt fibre, 2-5 parts of modifying agent, 25-40 parts of polyurethane rubber, 55-75 parts of starch, 0.3-0.8 parts of coupling agent,
3-5 parts of crosslinking agent, 5-10 parts of polyvinyl alcohol；The modifying agent forms mixed for acrylic acid hydroxyl ester with dimethyl methyl phosphonate
Compound；The coupling agent is epoxy silane coupling, and the crosslinking agent is ethylene glycol dimethacrylate；The polyurethane
The degree of polymerization of rubber is 800-1200；The starch degree of polymerization is 800-1200.
2. environment-friendly materials according to claim 1, it is characterised in that acrylic acid hydroxyl ester and methylphosphonic acid in the modifying agent
The ratio between amount of material of dimethyl ester is 1 ︰ 1.
3. environment-friendly materials according to claim 1, it is characterised in that the degree of polymerization of the polyurethane rubber is 900-
1100。
4. environment-friendly materials according to claim 3, it is characterised in that the degree of polymerization of the polyurethane rubber is 1000.
5. environment-friendly materials according to claim 1, it is characterised in that the starch degree of polymerization is 900-1100.
6. environment-friendly materials according to claim 5, it is characterised in that the starch degree of polymerization is 1000.
7. a kind of preparation method of the environment-friendly materials as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nanometer basalt fibre is handled with coupling agent；
（2）Nanometer basalt fibre Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nanometer basalt fibre after cladding and starch processing for composite in the electric field after mixing, mixed
Material；（4）By mixture and polyurethane rubber, crosslinking agent, polyvinyl alcohol it is uniform after in processing for composite, obtain antifatigue
Environment-friendly materials.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric field strength is 0.5-2kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric field strength is 0.8-1.5kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field is put down for direction of an electric field is constant
Row electric field.
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| CN201711228336.3A CN107903612A (en) | 2017-11-29 | 2017-11-29 | A kind of antifatigue environment-friendly materials and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841166A (en) * | 2018-07-11 | 2018-11-20 | 安徽嘉明新材料科技有限公司 | A kind of degradable TPU packaging film |
| CN111777688A (en) * | 2020-07-16 | 2020-10-16 | 抚顺天成环保科技有限公司 | Starch phosphate and application thereof |
-
2017
- 2017-11-29 CN CN201711228336.3A patent/CN107903612A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841166A (en) * | 2018-07-11 | 2018-11-20 | 安徽嘉明新材料科技有限公司 | A kind of degradable TPU packaging film |
| CN111777688A (en) * | 2020-07-16 | 2020-10-16 | 抚顺天成环保科技有限公司 | Starch phosphate and application thereof |
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