CN106380764A - Functional biodegradable material and preparation method thereof - Google Patents
Functional biodegradable material and preparation method thereof Download PDFInfo
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- CN106380764A CN106380764A CN201610781119.6A CN201610781119A CN106380764A CN 106380764 A CN106380764 A CN 106380764A CN 201610781119 A CN201610781119 A CN 201610781119A CN 106380764 A CN106380764 A CN 106380764A
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a functional biodegradable material and a preparation method thereof and belongs to the field of starch modification technology. The functional biodegradable material is prepared from the following raw materials (by weight): 30-65 parts of bio-based resin, 0-10 parts of a vapor-phase rust inhibitor, 0.5-1 part of an auxiliary agent, 5-25 parts of a plasticizer and 0-80 parts of plastic starch. The functional biodegradable material has the following advantages: raw material cost is low; degradation period and rust-proof life are controllable; mechanical properties are high; and energy is saved and the environment is protected. Meanwhile, the invention provides a simple and feasible preparation method, which is beneficial to industrial production.
Description
Technical field
The present invention relates to a kind of functionalization biodegradation material and preparation method thereof, belong to starch conversion technical field.
Background technology
Commercially available volatile rust preventive material has volatile rust preventive paper, volatile rust prevention liquid and petroleum base gas phase anti-tarnishing film, they
Critically important effect is played on the rust prevention packaging of metal material.But how these products are with petroleum material polyethylene, polypropylene etc.
As carrier, add that these products cannot reclaim, thus result in white pollution, be urgently to be resolved hurrily asking for environmental protection
Topic.For existing separated packaging material, degradation cycle cannot be carried out artificially adjusting and controlling, and mechanical property also tends to reach
Mark.
Therefore, the biodegradation material of functionalization is badly in need of being researched and developed and improving.
Content of the invention
It is an object of the invention to provide a kind of functionalization biodegradation material, its cost of material is low, degradation cycle and antirust
Phase is controlled, high mechanical properties, energy-conserving and environment-protective；Invention also provides simple preparation method, beneficial to industrialized production.
Functionalization biodegradation material of the present invention, is made up of the raw material of following parts by weight：
Described bio-based resin is polyvinyl alcohol (PVA), polylactic acid (PLA), poly butyric ester (PHB), poly-succinic
Butanediol ester (PBS), adipic acid-p-phthalic acid-fourth two ester copolymer (PBAT), polyhydroxyalkanoate (PHA) or poly- carbon
Acid esters (PPC).
Described vapor phase inhibitor (VIC) is formic acid dioctyl ester, cyclohexylamine, ortho-nitrophenol sodium salt, BTA, monoethanol
Amine, sodium benzoate, monoethanolamine benzoate, phytic acid, triethanolamine, fatty acid hexanamine, phosphoric acid cyclohexylamine, decanedioic acid three second
Alcohol amine salt, borate, hexamethylenamine, decanedioic acid sodium, lauric acid two hexanol amide borate, hexamethylenetetramine or sodium tetraborate
In multiple mixture.
Described auxiliary agent is by the material composition of following weight percentage：
(1) antibiotic bacteriostat：Nano-silver ionic fluorite, sodium alginate, shitosan, trimethyl, triethyl group or three normal-butyls
Quaternary ammonium salt, 5-10%；
(2) lubricant：Calcium stearate, zinc stearate, polyoxyethylene ester, oleamide, erucyl amide, stearic acid amide or
Dimethicone, 25-45%；
(3) antioxidant：Antioxidant 1010, antioxidant 1016, irgasfos 168, antioxidant 300, antioxidant 330, antioxidant
TZP or antioxidant BHT, 20-45%；
(4) nucleator：Calcium Carbonate, silicon dioxide, Pulvis Talci or montmorillonite, 5-10%；
(5) surfactant：Silane coupler, titanate coupling agent, boric acid ester coupler, sucrose fatty acid ester or poly- second
Alkene ether lauryl ether, 10-15.
Described processing aid should not be underestimated for the contribution margin of integral formula, and the function for product has adjustment effect.
Described plasticiser be propylene glycol, glyceryl triacetate, Polyethylene Glycol, Methanamide, acetamide, triethyl citrate,
Tributyl citrate, the acid of lemon lemon, mono stearate glyceryl ester, N- hydroxyethyl formamide, hydroxyalkyl Methanamide, second two support diformamide
Or the multiple mixture in fatty acid amide dihydroxylic alcohols.
The preparation method of described functionalization biodegradation material, is to mix raw material, stirs 10- at 45-120 DEG C
Then mixed material is carried out melt extruding pelletize by 60min, and prilling temperature is 40-230 DEG C.Can be used for after pelletize blown film,
Injection, sheet material, foaming, multi-layer co-extruded etc..
Prepared functionalization biodegradation material be monolayer, two layers, three layers or five layers, you can to make mono-material, monolayer
The products such as film are it is also possible to make three layers, five-layer co-squeezing film and biaxial tension, they are：A or A/AVIC or A/B-VIC or A/B/
C-VIC or A/B/C/B/A-VIC, wherein, VIC is gas-phase slow-release oxidant layer, the also referred to as contact layer of wrapping material, and A is therein arbitrary
Kind of bio-based resin, and B, C can be then other another kind bio-based resins, such as PLA-VIC or PVA-VIC, PBS-VIC or
PHA/PVA-VIC, PLA/PVA-VIC etc..
Functionalization biodegradation material of the present invention, is with bio-based resin as carrier, such as PLA, PVA, PPC,
PBS, PHA, PBAT etc., to control degradation time with volatile rust preventive material VIC (may also be referred to as biological decomposition regulator), and
Add various processing aids, the mutual synergism of each group split-phase, prepared material is used for preparing film, sheet material, foaming biaxial tension again
Deng product, the rust prevention packaging for metal material and other article of everyday use, artware, the packaging of chemicals, there is complete biology
Degradability, overcome in prior art the non-biodegradable of the material of preparation, it is to avoid causes white pollution.
When the vapour phase inhibitor consumption in composition of raw materials gets 0 value, the functionalization biodegradation material of preparation can be made
For high-barrier packaging material, degradation cycle is controlled, can be used for apparel textile, daily the articles for daily use, industrial goods, chemicals,
The fields such as ornament materials cuticula.
The invention has the advantages that：
(1) functionalization biodegradation material of the present invention, cost of material is low, and degradation cycle and rust-proof life are controlled, prevents
The rust cycle reached half a year to 5 years；
(2) functionalization biodegradation material of the present invention, by the coordination of each component it is achieved that the melting of material is squeezed
Go out, mechanical property is significantly improved；
(3) functionalization biodegradation material of the present invention, anti-bacterial refreshing is good, and energy-conserving and environment-protective are it is adaptable to existing
The processed and applied of the equipment such as blown film, curtain coating and injection；
(4) preparation method of functionalization biodegradation material of the present invention is simple, beneficial to industrialized production.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the enforcement of the present invention.
Embodiment 1
(1) prepare raw material：
- 1,799 30 parts of polyvinyl alcohol, 2 parts of formic acid dioctyl ester, 1 part of cyclohexylamine, 1 part of ortho-nitrophenol sodium salt, 0.5 part of auxiliary agent,
3 parts of propylene glycol, 2 parts of glyceryl triacetate, 20 parts of plasticity starch.
Described auxiliary agent is by the material composition of following weight percentage：
1. antibiotic bacteriostat：Nano-silver ionic fluorite, 5%；
2. lubricant：Calcium stearate, 45%；
3. antioxidant：Antioxidant 1010,25%；
4. nucleator：Calcium Carbonate, 10%；
5. surfactant：Silane coupler, 15%.
(2) preparation of functionalization biodegradation material：Put into after first the auxiliary agent described in step (1) proportionally being weighed up
In retort, heat while stirring, after melting at 45 DEG C, cooling is taken out standby.Then by other raw materials with ready help
Agent mixing is put in high speed mixer, stirs in intensification, mixes 30min, then by mixed material at 45-120 DEG C
It is cooled to 20 DEG C, places 12 hours at room temperature, be finally putting in the single screw rod with high flexibility shearing or dual-screw pelletizer
Carry out extruding pelletization, prilling temperature controls at 45-190 DEG C, then this particle is blown out single-layer gas-phase antirusting film.
Embodiment 2
(1) prepare raw material：
65 parts of polylactic acid, 4 parts of BTA, 6 parts of monoethanolamine, 10 parts of auxiliary agent, lemon lemon acid 5 parts, single-stearic acid glycerol
3 parts of ester, 4 parts of N- hydroxyethyl formamide, 1 part of hydroxyalkyl Methanamide, second two 12 parts of diformamide of support, 80 parts of plasticity starch.
Described auxiliary agent is by the material composition of following weight percentage：
1. antibiotic bacteriostat：Sodium alginate, 10%；
2. lubricant：Polyoxyethylene ester, 25%；
3. antioxidant：Irgasfos 168,45%；
4. nucleator：Silicon dioxide, 5%；
5. surfactant：Titanate coupling agent, 15.
(2) preparation of functionalization biodegradation material：Put into after first the auxiliary agent described in step (1) proportionally being weighed up
In retort, heat while stirring, after melting at 60 DEG C, cooling is taken out standby.Then by other raw materials with ready help
Agent mixing is put in high speed mixer, stirs in intensification, mixes 60min, then by mixed material at 45-120 DEG C
It is cooled to 20 DEG C, places 12 hours at room temperature, be finally putting in the single screw rod with high flexibility shearing or dual-screw pelletizer
Carry out extruding pelletization, prilling temperature controls at 45-210 DEG C, then this particle is blown out single-layer gas-phase antirusting film.
Embodiment 3
(1) prepare raw material：
40 parts of polyhydroxyalkanoate, 1 part of phytic acid, 3 parts of triethanolamine, 0.5 part of auxiliary agent, 3 parts of acetamide, Fructus Citri Limoniae triethylenetetraminehexaacetic acid
7 parts of ester, 35 parts of plasticity starch.
Described auxiliary agent is by the material composition of following weight percentage：
1. antibiotic bacteriostat：Shitosan, 10%；
2. lubricant：Oleamide, 30%；
3. antioxidant：Antioxidant TZP, 40%；
4. nucleator：Pulvis Talci, 8%；
5. surfactant：Sucrose fatty acid ester, 12%.
(2) preparation of functionalization biodegradation material：Put into after first the auxiliary agent described in step (1) proportionally being weighed up
In retort, heat while stirring, after melting at 60 DEG C, cooling is taken out standby.Then by other raw materials with ready help
Agent mixing is put in high speed mixer, stirs in intensification, mixes 60min at 45-95 DEG C, then will be cold for mixed material
But to 20 DEG C, place 12 hours at room temperature, be finally putting in the single screw rod with high flexibility shearing or dual-screw pelletizer
Row extruding pelletization, prilling temperature controls at 45-95 DEG C, then this particle is blown out single-layer gas-phase antirusting film.
Embodiment 4
(1) prepare raw material：
- 1,788 55 parts of polyvinyl alcohol, 1 part of hexamethylenamine, 2 parts of decanedioic acid sodium, 3 parts of hexanol amide borate of lauric acid two,
1 part of hexamethylenetetramine, 1 part of sodium tetraborate, 0.5 part of auxiliary agent, 3 parts of Methanamide, 4 parts of Polyethylene Glycol.
Described auxiliary agent is by the material composition of following weight percentage：
1. antibiotic bacteriostat：Three normal-butyl quaternary ammonium salts, 8%；
2. lubricant：Dimethicone, 40%；
3. antioxidant：Antioxidant BHT, 35%；
4. nucleator：Montmorillonite, 6%；
5. surfactant：Polyvinylether lauryl ether, 13%.
(2) preparation of functionalization biodegradation material：Put into after first the auxiliary agent described in step (1) proportionally being weighed up
In retort, heat while stirring, after melting at 60 DEG C, cooling is taken out standby.Then by other raw materials with ready help
Agent mixing is put in high speed mixer, stirs in intensification, mixes 60min at 45-95 DEG C, then will be cold for mixed material
But to 20 DEG C, place 12 hours at room temperature, be finally putting in the single screw rod with high flexibility shearing or dual-screw pelletizer
Row extruding pelletization, prilling temperature controls at 45-190 DEG C, then this particle is blown out high-isolating packaging film.
Embodiment 5
It is prepared according to the material variety in embodiment 3 and embodiment 4 and consumption respectively, then respectively material is put into
In high speed mixer, stir in intensification, mix 60min at 45-95 DEG C, then mixed material is cooled to 20 DEG C,
Place 12 hours at room temperature, be finally putting in the single screw rod comminutor with high flexibility shearing and carry out extruding pelletization.
Obtain two kinds of particles are separately added in two layers of coextrusion film blowing machine and blow out 30-100nm thin film, in this thin film, outward
Layer no vapor phase inhibitor, internal layer presses close to wrapping material layer as antirust coat, and this bilayer film has antirust time than single thin film
Longer effect.
Claims (7)
1. a kind of functionalization biodegradation material is it is characterised in that be made up of the raw material of following parts by weight：
2. functionalization biodegradation material according to claim 1 it is characterised in that：Bio-based resin be polyvinyl alcohol,
Polylactic acid, poly butyric ester, poly butylene succinate, adipic acid-p-phthalic acid-fourth two ester copolymer, poly- hydroxyl fat
Fat acid esters or Merlon.
3. functionalization biodegradation material according to claim 1 it is characterised in that：Vapor phase inhibitor is that formic acid two is pungent
Ester, cyclohexylamine, ortho-nitrophenol sodium salt, BTA, monoethanolamine, sodium benzoate, monoethanolamine benzoate, phytic acid, three second
Hydramine, fatty acid hexanamine, phosphoric acid cyclohexylamine, decanedioic acid triethanolamine salt, borate, hexamethylenamine, decanedioic acid sodium, Laurel
Multiple mixture in sour two hexanol amide borates, hexamethylenetetramine or sodium tetraborate.
4. functionalization biodegradation material according to claim 1 it is characterised in that：Auxiliary agent is by following weight percentage
Material composition：
(1) antibiotic bacteriostat：Nano-silver ionic fluorite, sodium alginate, shitosan, trimethyl, triethyl group or three normal-butyl quaternary ammoniums
Salt, 5-10%；
(2) lubricant：Calcium stearate, zinc stearate, polyoxyethylene ester, oleamide, erucyl amide, stearic acid amide or diformazan
Base silicone oil, 25-45%；
(3) antioxidant：Antioxidant 1010, antioxidant 1016, irgasfos 168, antioxidant 300, antioxidant 330, antioxidant TZP or
Antioxidant BHT, 20-45%；
(4) nucleator：Calcium Carbonate, silicon dioxide, Pulvis Talci or montmorillonite, 5-10%；
(5) surfactant：Silane coupler, titanate coupling agent, boric acid ester coupler, sucrose fatty acid ester or polyvinylether
Lauryl ether, 10-15.
5. functionalization biodegradation material according to claim 1 it is characterised in that：Plasticiser is propylene glycol, triacetic acid
Glyceride, Polyethylene Glycol, Methanamide, acetamide, triethyl citrate, tributyl citrate, the acid of lemon lemon, single-stearic acid glycerol
Ester, N- hydroxyethyl formamide, hydroxyalkyl Methanamide, second two support the multiple mixing in diformamide or fatty acid amide dihydroxylic alcohols
Thing.
6. a kind of arbitrary described functionalization biodegradation material of claim 1-5 preparation method it is characterised in that：By raw material
Mixing, stirs 10-60min at 45-120 DEG C, then carries out melt extruding pelletize by mixed material, prilling temperature is
40-230℃.
7. functionalization biodegradation material according to claim 6 preparation method it is characterised in that：Prepared functionalization
Biodegradation material be monolayer, two layers, three layers or five layers.
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| CN201610781119.6A CN106380764A (en) | 2016-08-31 | 2016-08-31 | Functional biodegradable material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868421A (en) * | 2017-12-21 | 2018-04-03 | 苏州星火丰盈环保包装有限公司 | A kind of degradable antirust bag and preparation method thereof |
| CN108059807A (en) * | 2018-01-23 | 2018-05-22 | 合肥峰腾节能科技有限公司 | It is a kind of for environment-friendly materials of electronic product and preparation method thereof |
| CN108219411A (en) * | 2018-01-03 | 2018-06-29 | 广东天元实业集团股份有限公司 | Biodegradable courier bag material |
| CN108285605A (en) * | 2018-01-24 | 2018-07-17 | 合肥同佑电子科技有限公司 | A kind of degradable type shell of capacitor high temperature resistant and preparation method thereof |
| CN108997689A (en) * | 2018-08-24 | 2018-12-14 | 张万虎 | A kind of fully bio-degradable volatile rust preventive material and its application |
| CN109021474A (en) * | 2018-07-28 | 2018-12-18 | 广东龙道新材料有限公司 | A kind of full biodegradable novel plastic |
| CN110885541A (en) * | 2019-12-18 | 2020-03-17 | 河北环瑞化工有限公司 | Biodegradable polylactic acid-based antirust master batch and preparation method thereof |
| CN115057107A (en) * | 2022-08-02 | 2022-09-16 | 山西农业大学 | Fruit and vegetable preservative film and preparation method thereof |
| CN115895048A (en) * | 2022-11-25 | 2023-04-04 | 维希艾环保新材料(上海)股份有限公司 | Antirust master batch and preparation method thereof |
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| JP2003165180A (en) * | 2001-11-30 | 2003-06-10 | Taihei Paper Mfg Co Ltd | Rustproof sheet |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868421A (en) * | 2017-12-21 | 2018-04-03 | 苏州星火丰盈环保包装有限公司 | A kind of degradable antirust bag and preparation method thereof |
| CN108219411A (en) * | 2018-01-03 | 2018-06-29 | 广东天元实业集团股份有限公司 | Biodegradable courier bag material |
| CN108059807A (en) * | 2018-01-23 | 2018-05-22 | 合肥峰腾节能科技有限公司 | It is a kind of for environment-friendly materials of electronic product and preparation method thereof |
| CN108285605A (en) * | 2018-01-24 | 2018-07-17 | 合肥同佑电子科技有限公司 | A kind of degradable type shell of capacitor high temperature resistant and preparation method thereof |
| CN109021474A (en) * | 2018-07-28 | 2018-12-18 | 广东龙道新材料有限公司 | A kind of full biodegradable novel plastic |
| CN108997689A (en) * | 2018-08-24 | 2018-12-14 | 张万虎 | A kind of fully bio-degradable volatile rust preventive material and its application |
| CN110885541A (en) * | 2019-12-18 | 2020-03-17 | 河北环瑞化工有限公司 | Biodegradable polylactic acid-based antirust master batch and preparation method thereof |
| CN110885541B (en) * | 2019-12-18 | 2021-09-07 | 河北环瑞化工有限公司 | Biodegradable polylactic acid-based antirust master batch and preparation method thereof |
| CN115057107A (en) * | 2022-08-02 | 2022-09-16 | 山西农业大学 | Fruit and vegetable preservative film and preparation method thereof |
| CN115057107B (en) * | 2022-08-02 | 2023-07-04 | 山西农业大学 | Fruit and vegetable preservative film and preparation method thereof |
| CN115895048A (en) * | 2022-11-25 | 2023-04-04 | 维希艾环保新材料(上海)股份有限公司 | Antirust master batch and preparation method thereof |
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