CN107936308A - A kind of high-impact degradation plastic and preparation method thereof - Google Patents

A kind of high-impact degradation plastic and preparation method thereof Download PDF

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Publication number
CN107936308A
CN107936308A CN201711226562.8A CN201711226562A CN107936308A CN 107936308 A CN107936308 A CN 107936308A CN 201711226562 A CN201711226562 A CN 201711226562A CN 107936308 A CN107936308 A CN 107936308A
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parts
starch
degradation plastic
barium sulfate
electric field
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舒春柳
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Sichuan Lizhi Jiuchuang Intellectual Property Operations Ltd
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Sichuan Lizhi Jiuchuang Intellectual Property Operations Ltd
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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
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of high-impact degradation plastic and preparation method thereof, including following parts by weight raw material to be prepared：55 75 parts of starch, 5 10 parts of nano barium sulfate, 58 parts of modifying agent, 30 50 parts of acrylic rubber, 35 parts of coupling agent, 0.1 0.3 parts of crosslinking agent, 13 parts of sodium trimetaphosphate；The present invention is for composite by the nano barium sulfate Jing Guo specific aim modification and starch, and nano barium sulfate is dispersed in starch system, and obtained degradation plastic excellent shock resistance, is conducive to application of the starch in more areas.

Description

A kind of high-impact degradation plastic and preparation method thereof
Technical field
The present invention relates to modified material field, and in particular to a kind of high-impact degradation plastic 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 shock resistance, the starch without impact modification has been difficult to meet Demand, thus, impact modification is carried out to starch and is necessitated.It is numerous to the impact modification processing method species of starch now More, modified effect is also fine, and especially with the appearance and application of nano material, the impact 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, shock resistance 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.During impact modification is carried out, nano material is disperseed Inequality can influence its shock resistance effect, and obtained modified material impact resistance is relatively low, 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 starch plastic impact resistance poor, there is provided a kind of high-impact can drop Solve plastics and preparation method thereof；The present invention is for composite by the nano barium sulfate Jing Guo specific aim modification and starch, and makes Nano barium sulfate is dispersed in starch system, and obtained degradation plastic excellent shock resistance, is conducive to starch more Application in multi-field.
In order to realize foregoing invention purpose, the present invention provides a kind of high-impact degradation plastic, including following parts by weight Raw material are prepared：55-75 parts of starch, 5-10 parts of nano barium sulfate, 5-8 parts of modifying agent, 30-50 parts of acrylic acid Ester rubber, 3-5 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of sodium trimetaphosphate.
A kind of above-mentioned high-impact degradation plastic, can increase resin material impact resistance according to nano barium sulfate and crosslinking Basic principle, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nano barium sulfate with forming sediment Compatibility between powder, and make nano barium sulfate disperse evenly, to make impact resistance of the nano barium sulfate to starch in starch Humidification is more preferable, also by control the degree of polymerization of starch make modified degradation plastic impact resistance and processability it Between reach optimum balance relation so that the degradation plastic made is under conditions of with excellent impact resistance, it may have Excellent processability, allows it to be applied in more areas.
A kind of above-mentioned high-impact degradation plastic, wherein, the nano barium sulfate particle diameter is 10-80nm；Nanometer sulfuric acid Granellae footpath is smaller, and dispersiveness is poorer, and nano barium sulfate particle diameter is bigger, and the shock resistance humidification to starch is poorer；Preferably, institute The nano barium sulfate particle diameter stated is 30-50nm；Most preferably, the nano barium sulfate particle diameter is 40nm.
A kind of above-mentioned high-impact degradation plastic, wherein, the modifying agent is epoxychloropropane and methyl acrylate group Into mixture；The modifying agent can improve the compatibility of nano barium sulfate and starch and on nano barium sulfate surface Polar group is formed, beneficial to scattered；Preferably, in the modifying agent material of epoxychloropropane and methyl acrylate amount it Than for 1 ︰ 2.
A kind of above-mentioned high-impact degradation plastic, wherein, the degree of polymerization of acrylic rubber is bigger, then degradable after being crosslinked The impact resistance of plastics is poorer, and processability is better, and the polymer of acrylic rubber is smaller, then degradation plastic is anti-after being crosslinked Impact is better, and processability is poorer, therefore, selects the rational acrylic rubber degree of polymerization, is balance impact resistance and processing The important means of property.The degree of polymerization of the acrylic rubber is 180-280；Preferably, the acrylic rubber The degree of polymerization is 200-250；Optimal, the degree of polymerization of the acrylic rubber is 230；By preferred, what is obtained is degradable Plastics both have excellent impact resistance, it may have preferable processability, is adapted to.
Wherein, the starch degree of polymerization is 900-1500；Preferably, the degree of polymerization of the starch is 1000-1400；Most Preferably, the degree of polymerization of the starch is 1200；By preferred, obtained degradation plastic both has excellent shock resistance Property, it may have preferable processability.
A kind of above-mentioned high-impact degradation plastic, wherein, the coupling agent is epoxy silane coupling；Epoxy group silicon Alkane can increase the compatibility between nano barium sulfate and starch and modifying agent, improve the shock resistance of degradation plastic.
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 impact resistance of degradation plastic.
A kind of above-mentioned high-impact degradation plastic, wherein, its raw material further includes dispersant, plasticizer, antistatic additive, dye One or more auxiliary agents in toner, brightener；Above-mentioned auxiliary agent can improve the processability of degradation plastic, increase its feature Deng effect, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of system of high-impact degradation plastic Preparation Method, comprises the following steps：
（1）Nano barium sulfate is handled with coupling agent；
（2）Nano barium sulfate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano barium sulfate after cladding and starch processing for composite in the electric field after mixing, mixture is obtained；
（4）By mixture and acrylic rubber, crosslinking agent, sodium trimetaphosphate after mixing in processing for composite, obtain High-impact degradation plastic.
A kind of preparation method of high-impact degradation plastic, first carries out coupling processing with coupling agent to nano barium sulfate, increases Ghana's nano-barium sulfate and modifying agent, the compatibility of starch；Processing is modified to nano barium sulfate with modifying agent again, and in its table Face forms polar group；Finally the polar group in nano barium sulfate surface and starch chain is set to polarize using external electric field, it is powered, lead to Repelling each other between electric charge or attracting principle are crossed, also can be with the polar group on starch chain while making nano barium sulfate dispersed Group it is bonded so that the shock resistance enhancing effect of nano barium sulfate is farthest embodied, so as to get modified starch resist Impact significantly improves；The preparation method is simple and reliable, is suitable for extensive, the industrial metaplasia of high-impact degradation plastic Production.
A kind of preparation method of above-mentioned high-impact degradation plastic, wherein, it is preferred that step 1 carries out coupling processing process In can use ultrasonic wave aid in；Shaken by the high speed of ultrasonic wave, make nano barium sulfate dispersiveness more preferable, and have to coupling processing There is facilitation.
A kind of preparation method of above-mentioned high-impact degradation plastic, wherein, the electric field energy described in step 3 produces group Polarization, makes group powered, so as to promote the scattered and bonded effect of nano barium sulfate, improves the shock resistance of modified starch Property.
Preferably, the electric field strength is 0.5-2kv/m；Electric field strength is too small, and polarization effect is weak, to nano barium sulfate Dispersion effect it is poor；Electric field strength is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces displacement, right The arrangement of strand and the bonded shock resistance for having an impact, may be decreased degradation plastic；Most preferably, the electric field Intensity is 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, to the scattered and bonded facilitation of nano barium sulfate Best results.
Compared with prior art, beneficial effects of the present invention：
1st, high-impact degradation plastic of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes nano-sulfur Compatibility between sour barium and starch is more preferable, and the dispersiveness in starch is more preferable, and nano barium sulfate increases the impact resistance of starch Pretend with more preferable.
2nd, high-impact degradation plastic of the present invention is made modified by controlling the degree of polymerization of starch and acrylic rubber Degradation plastic reach optimum balance relation between impact resistance and processability, so as to get degradation plastic with excellent Under conditions of different impact resistance, it may have excellent processability.
3rd, the preparation method of high-impact degradation plastic of the present invention, using the polarization of external electric field, can promote nano-sulfur Sour barium is scattered and bonded in starch system, and the shock resistance enhancing effect of nano barium sulfate is more preferable, obtained degradation plastic Impact resistance higher.
4th, preparation method of the present invention is simple, reliable, is adapted to extensive, the industrialized production of high-impact degradation plastic.
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）8 parts of nano barium sulfate is handled with 0.5 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of epoxychloropropane and 4 parts of methyl acrylate Processing；
（3）It is in electric field strength after mixing by the starch that the nano barium sulfate after cladding is 1200 with 65 parts of the degree of polymerization Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Acrylic rubber, the 4 parts of dimethacrylate second of the mixture that step 3 is obtained and 40 parts of the degree of polymerization for 230 Diol ester, 2 parts of sodium trimetaphosphate are extruded after mixing, obtain high-impact degradation plastic.
Embodiment 2
（1）5 parts of nano barium sulfate is handled with 0.3 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 4 parts of epoxychloropropane and 4 parts of methyl acrylate Processing；
（3）It is being in electric field strength after mixing by the starch that the nano barium sulfate after cladding is 900 with 55 parts of the degree of polymerization Extruded in the electric field of 2.0kv/m, obtain mixture；
（4）Acrylic rubber, the 3 parts of dimethacrylate second of the mixture that step 3 is obtained and 50 parts of the degree of polymerization for 280 Diol ester, 3 parts of sodium trimetaphosphate are extruded after mixing, obtain high-impact degradation plastic.
Embodiment 3
（1）10 parts of nano barium sulfate is handled with 0.8 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of epoxychloropropane and 3 parts of methyl acrylate Processing；
（3）It is being in electric field strength after mixing by the starch that the nano barium sulfate after cladding is 1500 with 75 parts of the degree of polymerization Extruded in the constant parallel electric field of the direction of an electric field of 0.5kv/m, obtain mixture；
（4）Acrylic rubber, the 5 parts of dimethacrylate second of the mixture that step 3 is obtained and 30 parts of the degree of polymerization for 180 Diol ester, 1 part of sodium trimetaphosphate are extruded after mixing, obtain high-impact degradation plastic.
Comparative example 1
（1）8 parts of nano barium sulfate is handled with 0.5 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is mixed with 5 parts of dispersant, the starch that 65 parts of the degree of polymerization is 1200 Extruded after uniformly in the constant parallel electric field of the direction of an electric field that electric field strength is 1.2kv/m, obtain mixture；
（3）Acrylic rubber, the 4 parts of dimethacrylate second of the mixture that step 2 is obtained and 40 parts of the degree of polymerization for 230 Diol ester, 2 parts of sodium trimetaphosphate are extruded after mixing, obtain degradation plastic.
Comparative example 2
（1）8 parts of nano barium sulfate is handled with 0.5 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of epoxychloropropane and 4 parts of methyl acrylate Processing；
（3）The propylene for being 120 by starch that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 900,40 parts of the degree of polymerization Acid esters rubber, 4 parts of ethylene glycol dimethacrylate, 2 parts of sodium trimetaphosphate are extruded after mixing, are obtained degradable Plastics.
Comparative example 3
（1）8 parts of nano barium sulfate is handled with 0.5 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is carried out at cladding with 2 parts of polystyrene and 4 parts of methyl acrylate Reason；
（3）It is in electric field strength after mixing by the starch that the nano barium sulfate after cladding is 1200 with 65 parts of the degree of polymerization Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Acrylic rubber, the 4 parts of dimethacrylate second of the mixture that step 3 is obtained and 40 parts of the degree of polymerization for 230 Diol ester, 2 parts of sodium trimetaphosphate are extruded after mixing, obtain degradation plastic.
Comparative example 4
（1）8 parts of nano barium sulfate is handled with 0.5 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of epoxychloropropane and 4 parts of methyl acrylate Processing；
（3）By the acrylic rubber of the nano barium sulfate after cladding and 40 parts of the degree of polymerization for 230,4 parts of dimethacrylates The starch that glycol ester, 2 parts of sodium trimetaphosphate, 65 parts of the degree of polymerization are 1200 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 degradation plastic.
Comparative example 5
（1）8 parts of nano barium sulfate is handled with 0.5 part of epoxy radicals silicone hydride；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of epoxychloropropane and 4 parts of methyl acrylate Processing；
（3）It is in electric field strength after mixing by the starch that the nano barium sulfate after cladding is 800 with 65 parts of the degree of polymerization Extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）The mixture that step 3 is obtained and 40 parts of the degree of polymerization are 150 acrylic rubber, 2 parts of sodium trimetaphosphate, 4 Part ethylene glycol dimethacrylate is extruded after mixing, obtains degradation plastic.
By the degradation plastic in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data are as follows：
Performance Notch impact strength（KJ/m2） Processability
Embodiment 1 11.5 ++++
Embodiment 2 10.7 ++++
Embodiment 3 11.3 ++++
Comparative example 1 7.8 ++++
Comparative example 2 8.5 ++++
Comparative example 3 9.4 ++++
Comparative example 4 7.2 ++++
Comparative example 5 11.6 ++
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the degradation plastic of the present invention being prepared in embodiment 1-3, nanometer sulfuric acid Barium is uniformly dispersed, good with the compatibility of starch, degradation plastic good impact resistance, and processability is good；And in comparative example 1, it is not used Modifying agent is modified nano barium sulfate processing, although adding dispersant, nano barium sulfate dispersion effect is poor, with starch Poor compatibility, the impact resistance of degradation plastic significantly reduces；Not processing for composite in the electric field, nanometer in comparative example 2 Barium sulfate dispersion effect is poor, and the impact resistance of degradation plastic significantly reduces；Modifying agent is not the application defined in comparative example 3 , nano barium sulfate dispersion effect is poor, and the impact resistance of degradation plastic significantly reduces；Cross-linking reaction equally exists in comparative example 4 Carried out in electric field, electric field has a negative impact cross-linking reaction, so as to get degradation plastic impact resistance reduce；Comparative example The starch and the acrylic rubber degree of polymerization used in 5 is too small, although impact resistance increased after compound, its processability is shown Writing reduces, and is unfavorable for the application of high-impact degradation plastic.

Claims (10)

1. a kind of high-impact degradation plastic, it is characterised in that be prepared including following parts by weight raw material：55-75 parts Starch, 5-10 parts of nano barium sulfate, 5-8 parts of modifying agent, 30-50 parts of acrylic rubber, 3-5 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of sodium trimetaphosphate；The modifying agent is epoxychloropropane and methyl acrylate composition Mixture；The coupling agent is epoxy silane coupling, and the crosslinking agent is ethylene glycol dimethacrylate；The propylene The degree of polymerization of acid esters rubber is 180-280；The starch degree of polymerization is 900-1500.
2. degradation plastic according to claim 1, it is characterised in that epoxychloropropane and acrylic acid in the modifying agent The ratio between amount of material of methyl esters is 1 ︰ 2.
3. degradation plastic according to claim 1, it is characterised in that the degree of polymerization of the acrylic rubber is 200- 250。
4. degradation plastic according to claim 3, it is characterised in that the degree of polymerization of the acrylic rubber is 230.
5. degradation plastic according to claim 1, it is characterised in that the starch degree of polymerization is 1000-1400.
6. degradation plastic according to claim 5, it is characterised in that the starch degree of polymerization is 1200.
7. a kind of preparation method of the degradation plastic as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nano barium sulfate is handled with coupling agent；
（2）Nano barium sulfate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano barium sulfate after cladding and starch processing for composite in the electric field after mixing, mixture is obtained；
（4）By mixture and acrylic rubber, crosslinking agent, sodium trimetaphosphate after mixing in processing for composite, obtain High-impact degradation plastic.
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.
CN201711226562.8A 2017-11-29 2017-11-29 A kind of high-impact degradation plastic and preparation method thereof Withdrawn CN107936308A (en)

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Application Number Priority Date Filing Date Title
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CN107936308A true CN107936308A (en) 2018-04-20

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