CN1047783C - Reversible cross-linked starch resin compound and its preparation method - Google Patents
Reversible cross-linked starch resin compound and its preparation method Download PDFInfo
- Publication number
- CN1047783C CN1047783C CN 96104665 CN96104665A CN1047783C CN 1047783 C CN1047783 C CN 1047783C CN 96104665 CN96104665 CN 96104665 CN 96104665 A CN96104665 A CN 96104665A CN 1047783 C CN1047783 C CN 1047783C
- Authority
- CN
- China
- Prior art keywords
- starch
- acrylic acid
- described composition
- resin
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a starch degrading resin compound, a preparation method thereof and application thereof. The starch degrading resin compound contains hydroxypropyl starch mother particles, ethene-acrylic-acid copolymers, catalysts, reversible crosslinking agents and synthetic resin. Because of the utilization of unique starch modifying agents, the reversible crosslinking agents and the multifunctional degradation catalysts, the starch degrading resin compound has the advantages of good mechanical property and favorable processing property, and can be widely used for film blowing, injection molding and relevant purposes.
Description
The present invention relates to a kind of Degradable Starch Resin composition, its preparation method and application, particularly a kind of new Degradable Starch Resin composition and method of making the same wherein contains unique starch conversion and reversible cross-linking agent and function degradation catalyst.This starch-resin has good mechanical properties and processing characteristics, can be widely used in blown film, injection and associated uses.
The large-scale commercial applications of plastics is used and is made waste plastic cause severe contamination to environment, and the pollution problem of researching and solving waste plastic has become the focus of research.One of method that solves is research and produces decomposable plastics to replace conventional plastic.One of them is that starch is added in the synthetic plastics as biological substance, because starch source is extensive, renewable, inexpensive, thereby the development of starch-resin comes into one's own day by day.At present, the addition manner of starch can be divided into three kinds: (A) starch is made an addition in the synthetic resins as granular filler, normally handle dry starch with silicoorganic compound and titanic acid ester, change the hydrophilic characteristics of starch, with the synthetic resins blend, because the particle diameter of starch is too big, so the too high meeting of starch content significantly damages mechanical property then, thereby the starch content of the finished product is mostly between 6-16%, and degradation property is bad; (B) make with starch and wetting ability synthetic resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer and other additive, this resinoid biological degradability is good, but water resisting property is poor, and product performance are influenced by ambient temperature very big, and poor processability, and price is higher; (C) with starch, polyethylene, ethylene-acrylic acid copolymer (EAA), softening agent adding under the condition of water, make starch pasting, make polyethylene, EAA blend with it simultaneously, extrude and remove granulation behind the superfluous water.The characteristics of this method are the gelatinizations of starch, blend is once finished, and make the application of wet starch become possibility, but the starch blending resin of this method processing, starch content is higher than at 25% o'clock, and mechanical performance of products obviously descends, and the processing of combinations and use are subjected to humidity effect bigger, when blown film, can not obtain thin film.Very fast embrittlement after storing under the exsiccant environment, the heat seal poor performance, this is because the distributional stability of starch is poor, after moisture content scatters and disappears, due to assembling again.Electron microscope observation finds that the dispersion granule size of starch is dispersed bad between 30-100 μ.Starch is a kind of strong polarity high molecular crystal material, all there is extremely strong hydrogen bond with intramolecularly between the molecule, synthetic resins commonly used such as polyethylene then are a kind of nonpolar polymkeric substance, therefore the consistency of improving starch and synthetic resins is to increase the starch addition, improves the key of blend mechanical property.In the prior art, mainly be to adopt EAA as increasing component, but studies show that EAA and starch are that part is compatible and belong to physical mixed substantially, therefore starch and synthetic resins mutually between cohesive force very little, separate easily mutually, this has just caused mechanical property bad, and is especially true when particularly starch content is high.Though modified starch such as hydroxypropylated starch, carboxymethyl starch etc. make moderate progress with the consistency of synthetic resins, cost height, other chemical modification method are all owing to the cost problem is difficult to practicality.
In the prior art, in order to promote the degraded of synthetic resins, add the salt of photosensitizers such as transition metal, but be difficult to play a role loseing under the condition of light, and since in soil micromolecule catalyst be easy to migration, ooze out, cause inactivation.Thereby the catalyzed degradation effect is not ideal.
As mentioned above, in the prior art, it is low to obtain cost, and decomposability is good, and the good Degradable Starch Resin of application performance.
The objective of the invention is to provide for the shortcoming that overcomes prior art a kind of preparation method of Degradable Starch Resin, it adopts active starch modifying agent to change the wetting ability of starch, and starch is easy to and the synthetic resins blend, realizes high starch filled.
The present invention introduces the reversible crosslink notion, improves starch and synthetic resins dispersiveness and phase interface viscous force mutually, thereby improves the mechanical property that high starch adds degradative resin greatly.
The present invention has also adopted a kind of degradation catalyst system, owing to form by Primary Catalysts, promotor and catalytic inhibitor, it not only has photodegradation, but also have significant heat and oxidative degradation performance, can destroy starch and polyolefinic phase structure within a short period of time, and polyolefin molecular weight is reduced, thereby finally can be utilized by Institute of Micro-biology fully.Therefore this kind Degradable Starch Resin has good degradation property.
Another object of the present invention provides degradable resin composition of the present invention and makes product.
According to the present invention, Degradable Starch Resin comprises following composition:
(A) the modified starch master batch that contains following ingredients of 20-80 (weight part);
The starch of 70-90 (weight part),
The active modifier of 3-15 (weight part),
The EAA of 2-5 (weight part),
The plasticizers of (2.5-15 weight part),
The alkaline additive of (0.5-4 weight part),
The flow ability modifying agent of (0.7-3 weight part),
The dispersion agent of (0.3-2 weight part),
The maleic anhydride grafted polyethylene modified resin of 3-8 (weight part);
(B) ethylene-acrylic acid copolymer of 4-20 (weight part);
(C) catalyzer of 1-4 (weight part);
(D) the reversible small molecules linking agent of 2-10 (weight part);
(E) synthetic resins of 13-60 (weight part).
According to method provided by the invention, the preparation of degradative resin may further comprise the steps:
(1) preparation of modified starch master batch:
With starch, properties-correcting agent, EAA, softening agent, flow ability modifying agent and alkaline additive react in twin screw extruder in proportion, extrude, granulation and getting, add the grain order and obtain graft starch for earlier starch, maleic anhydride grafted polyethylene modified resin and alkalescence being added reaction, second section feeding adds rest materials then, obtains having good thermoplastic modified starch master batch;
(2) preparation of polymer catalyst:
The EAA of high acrylic acid content is dissolved in the alkaline solution, stirs the salts solution that adds transition metal down, promptly have precipitation to separate out, reacted 2 hours down at 80 ℃, the washing drying son amount Primary Catalysts that secures satisfactory grades, its transport property is very little, and has the good mixing performance with synthetic resins; This Primary Catalysts and promotor, catalytic inhibitor are mixed in proportion;
(3) preparation of biodegradable starch-resin particle:
With the modified starch master batch, EAA, catalyzer, reversible cross-linking agent and synthetic resins mix in proportion the back at the twin screw extruder extruding pelletization, remove unnecessary moisture content simultaneously and obtain Degradable Starch Resin provided by the present invention.
The present invention has obtained satisfied result, the treated starch addition can be up to about 80% in the starch-resin, good processability also can be easy to be blow molded into film on the blow moulding equipment of routine, thickness reaches 5-10 μ, film-in starch be transformed into unformed body by crystallinity, and very high dispersiveness and dispersion stabilization are arranged.Under processing conditions, linking agent is inoperative, and at normal temperatures, plays crosslinked action, has good mechanical property.The easily shortcoming of migration of micromolecule catalyst has been avoided in the use of polymer catalyst system, has tangible light, heat and chemical degradation effect, and degradation speed and degradation rate significantly improve.
The present invention relates to a kind of preparation method of the modified starch master batch with good thermoplastic newly, it comprises:
The starch of 70-90 (weight part),
The active modifier of 3-15 (weight part),
The EAA of 2-5 (weight part)
The softening agent of (2.5-15 weight part),
(0.5-4 weight part) alkaline additive,
The flow ability modifying agent of (0.7-3 weight part),
The dispersion agent of (0.3-2 weight part),
The maleic anhydride grafted polyethylene modified resin of 3-8 (weight part);
Described starch can be W-Gum, potato starch, sweet potato starch, Sumstar 190, anionic starch and etherification starch, below the water content 14% (weight), the addition of starch in the modified starch master batch is 70-90% (W/W), preferably 70-80% (W/W).
Described active modifier is the Succinic anhydried derivative with chain alkyl, as the octenyl Succinic anhydried, laurylene base butyryl oxide, hexadecylene base Succinic anhydried, octadecylene base Succinic anhydried and lower molecular weight maleic anhydride graft polyhutadiene (1000-5000), addition 3-15% (W/W), preferably 10-15% (W/W).In the presence of alkali, this Succinic anhydried derivative easily and the hydroxyl in the starch react, generate the starch derivative of belt length chain, it has and synthetic resins good mixing performance, and this material can improve the stability of disperseing the starch phase greatly as upper layer, the product of acquisition good mechanical properties, because sex change is once to finish, can not increase processing cost simultaneously in forcing machine.
Described EAA mix to use as increasing, in order to increase the consistency with starch.Acrylic acid content among the EAA should be more than 20%, because it has the bigger body index that melts, can increase the flowability of modified starch, but the starch granularity is reduced, and can increase the consistency of starch and synthetic resins simultaneously.Addition 3-10%, preferably 6-8% (W/W).
Described softening agent is an ethylene glycol, propylene glycol and their lower molecular weight condenses, glycerine, sorbyl alcohol, wherein with the mixture (1: 1) of glycerine and sorbyl alcohol and single stearic acid glycerine lipoprotein be used effect preferably and cost than also much lower with glycerine.If single with glyceride be used effect preferably and cost than also much lower with glycerine.If list is used glycerine, though good plastification is arranged, glycerine easily oozes out (perspiration) under the condition of high humidity, and boiling point is relatively low, is easy to the high influence of volatilization and cost and uses.Use sorbyl alcohol as single, then plasticization effect is bad, and sorbyl alcohol is easily separated out crystallization.Addition 2.5-1.5% (W/W), 8-10% (W/W) preferably, the use of softening agent can not only make starch have good processing properties, improves the decomposition temperature of starch, can also stop the pasted starch crystallization, gives goods good unit elongation.、
Described alkaline additive is in order to promote the reaction of Succinic anhydried and starch, can also to promote the gelatinization of starch simultaneously.Sodium hydroxide commonly used, potassium hydroxide, addition is so that the system pH value is advisable about 1-4%, and be made into the aqueous solution use of 0.5-1% between 9-11.
Described flow ability modifying agent and dispersion agent are the sweet Shan ester of Stearinsaeure, oleic acid.Sorb ferment acid anhydride monostearate (Si Ben-60).Sorbitan mono-oleic acid ester (Si Ben-80).It can not only promote the flowability of starch; and can form layer protective layer on dispersive starch surface, this protects the consistency that improves starch and synthetic resins greatly, can also stop simultaneously to disperse starch to reassemble; addition 1-5% (W/W), preferably 3-5% (W/W).
Use method of the present invention, starch is joined in the twin screw extruder, with pump maleic anhydride grafted polyethylene modified resin, sodium hydroxide solution and properties-correcting agent are metered into respectively simultaneously, reacting by heating, again with EAA, softening agent and flow ability modifying agent and dispersion agent add at the forcing machine middle part, and vacuum is removed moisture content, extrude, granulation gets the modified starch master batch.Processing conditions: temperature: 90-100 ℃/120-130 ℃/120-130 ℃/120-130 ℃/130-140 ℃/120-130 ℃, rotating speed 200-300RPM, starch master batch require the high plasticizing of transparency evenly.Between the water content 5-8% (weight).The starch master batch that makes with method provided by the invention, dsc analysis shows, do not possessed crystallinity, has good thermoplastic, and fabulous consistency is arranged with synthetic resins, the starch addition is improved greatly, for the product that obtains the good physical mechanical property provides assurance, is one of key of the present invention.
According to the present invention, the modified starch master batch, EAA, reversible cross-linking agent, catalyzer (Primary Catalysts and promotor and inhibitor) and synthetic resins carry out blending reaction and get Degradable Starch Resin in twin screw extruder.
Wherein, described EAA provides active group for reversible crosslink simultaneously as increasing component.Acrylic acid content 5-15% among the EAA (W/W), preferably 5%, it not only has good consistency with synthetic resins, also has the favorable mechanical performance simultaneously.
Described catalyzer is the transition metal salt of ethylene-acrylic acid, mainly is molysite, mantoquita, cobalt salt and manganese salt.As Primary Catalysts, it has short reason free radical formation effect.Promotor is undersaturated compound, as oleic acid, low molecular weight polybutadiene, styrene-butadiene block copolymer (SBS) etc. has the material of unsaturated double-bond, this material can oxidation form superoxide and decompose the generation free radical under the effect of Primary Catalysts, cause polyolefinic degraded, make polyolefine form the small molecule segment that has carboxyl, carbonyl, hydroxyl isopolarity base, when molecular weight less than 3000 the time, proved and can have been decomposed fully, thereby improved the wherein natural decomposition ability of synthetic resins greatly by microorganism.Wherein also contain catalytic inhibitor, mainly be 2,6-di-tert-butyl methyl phenol (BHT, industrially also claim 264), four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester oxidation inhibitor such as (1010), catalyzer is not degraded in processing and storage process, guarantee use properties, addition depends on the length of required inductive phase, and catalyzer addition 1-4% (W/W) depends on desired degradation speed.
Described reversible cross-linking agent is an o-methoxybenzoic acid zinc, be characterized in being easy to mixing with starch and synthetic resins, and form ionic linkage between carboxyl on starch and the carboxyl among the EAA, and this ionic linkage is when heating (more than 140 ℃), zine ion can form salt with o-methoxybenzoic acid, can not cause the increase of melting body viscosity like this, can not bring processing difficulties, when temperature reduces, o-methoxybenzoic acid forms intramolecular hydrogen bond and discharges zine ion, form ionic linkage, strengthened starch and the synthetic resins interfacial adhesion between mutually greatly, can in system, form the structure of IPN, thereby improved the mechanical property of goods greatly, the addition 2-10% (W/W) of reversible cross-linking agent, preferably 5-8% (W/W).
Described synthetic resins is polyethylene, polypropylene and urethane resin, and vibrin preferably has small amount of polar group such as hydroxyl, and carboxyl or amino reach range of application as requested and decide.Film is with polyethylene, the polyurethane termoplastic elastomer of resin with polyethylene or hydroxylation.Injection based article polypropylene, vibrin.Addition 13-60% (W/W).
According to method of the present invention, with the modified starch master batch, EAA, catalyzer, reversible cross-linking agent and synthetic resins mix in twin screw extruder in proportion, fusion, reaction, extruding pelletization and getting.Under processing conditions, starch is dispersed in the synthetic resins, the CONTROL PROCESS condition, make starch form mutual dispersive microfacies structure mutually with synthetic resins mutually, more particularly the effect owing to properties-correcting agent has formed active group carboxyl (COOH) on the starch molecule, and in the synthetic resins because the hydroxyl of EAA or itself, make under the effect of reversible crosslink crosslinked, set up strong chemical bond mutually and between the synthetic resins phase at starch, greatly strengthened the phase interface cohesive force, the IPN structure that whole diagram of system is revealed run through network mutually, thereby show fabulous physical and mechanical properties down in that height is starch filled.This linking agent is different from traditional linking agent, although the tradition linking agent can strengthen mechanical property, but because the increase of molecular weight, viscosity increases, can bring processing difficulties, and cross-linking system of the present invention, form by physical crosslinking and chemically crosslinked, physical crosslinking derive from wherein select have a crystallinity segmental polymer substance, crystallinity disappears under processing conditions, has excellent flowing, and at normal temperatures, it can form crystallizing field with the part material in the modified starch, and this crystallizing field is equivalent to cross-linking set.Simultaneously,, can between starch and synthetic resins, form ionic linkage at normal temperatures, play strong crosslinked action, but under processing temperature, this key be destroyed by reversible cross-linking agent.The reversible crosslink system can play linking agent at normal temperatures as a result, but inoperative under processing conditions, has great superiority, and the introducing of this notion is one of key of the present invention.Dsc analysis shows that system has good thermostability, and 200 ℃ obvious decomposition can not take place in the past, illustrated that the thermostability of starch has improved greatly.This resin is made film, handle with acid-base solution, can be weightless, and also hot platform microscopic examination shows that also the melting of each phase is very even, demonstrates the feature that forms the IPN structure, this is unthinkable in traditional starch filled type resin.
According to the present invention, the introducing of degradation catalyst is in order to quicken the degraded of synthetic resins wherein, because the present invention adopts high molecular catalyzer, thereby has reduced migration, oozes out, and avoids inactivation, and is simultaneously splendid with the consistency of synthetic resins.The existence of promotor unsaturated materials can be quickened the catalyzed degradation process effectively in addition, and the existence of catalytic inhibitor simultaneously can make degradation process controlled.The result shows that this catalyst system has good light, heat and chemical degradation performance, even bury in soil, rubbish, most films also disappeared in 1 year, and checks through the degradation property of State Bureau of Environmental Protection Nanjing environmental protection institute and Taiwan industrial research institute.
According to the present invention, the production process of Degradable Starch Resin is that a very complicated polycomponent mixes, reaction process, each component all has different performances and function, bring into play maximum effect separately for making it, each step of technology must strictly be controlled, according to the present invention, processing temperature from feeding to die head 90-110 ℃/100-150 ℃/120-180 ℃/130-190 ℃/140-200 ℃/120-180 ℃, melt temperature 140-180 ℃, melt moisture content 5-6% (weight), rotating speed 250-400rpm, moment of torsion 50-90%.
The starch that makes by the inventive method falls resin and can be blow molded into film with traditional device of plastic processing, makes various refuse bags, shopping bag; packing bags etc. are injected into various hard products, are extruded into various containers; be widely used in the non-returnable container goods, the protection environment is had crucial meaning.
Degradable Starch Resin preparation method of the present invention has following advantage:
(A) owing to starch modifying agent, the effect of reversible cross-linking agent and relevant auxiliary agent make the starch addition improve greatly, and goods has superior physical and mechanical properties.
(B) available general-purpose equipment carries out goods processing, and complete processing is easy to control.
(C) introduce the notion of reversible crosslink, making combining between starch and the synthetic resins no longer is physical bond, but Chemical bond, and this process is once finished in forcing machine.
(D) existence of polymer catalyst system catalyzed degradation synthetic resins effectively not only, and avoided micromolecule catalyst easily to move, ooze out, do not have the shortcoming of living is realized efficient, low toxicity, controlled target.
(E) product has very good environment degradable performance, has solved the problem that synthetic resins can not be degraded in the present starch addition type resin, and experiment shows, this product 1 year overwhelming majority in physical environment disappears and with microorganism ten good affinities arranged.
(F) have low relatively cost, be easy to be accepted by market.
Embodiment 1.
EAA (20% acrylic acid content) 100 grams are dissolved in the 1000ml water that contains 12gNaOH, are heated to 80-90 ℃, treat that EAA dissolves fully.Under agitation add 45 then and restrain the solution that FERRIC CHLORIDE ANHYDROUS are dissolved in 500ml water, heat 80 ℃ and kept 2 hours, treat that replacement(metathesis)reaction finishes, filter, washing, the dry EAA (Fe that gets
3+) salt.
EAA (20% acrylic acid content) 100 gram is dissolved in the 1000ml alkaline solution that contains 12gNaOH, is heated to 80-90 ℃, treat that EAA dissolves fully after, under agitation add 47 gram CuCl
22H
2O is dissolved in the solution of 500ml water, and heat tracing 2 hours treats that replacement(metathesis)reaction finishes, and filters washing, the dry Cu that gets
2+(EAA) salt.
Make the alkaline solution of EAA equally with said process, add 66 gram CoCl then
2+6H
2The solution of O, heat tracing 2 hours after reaction finishes, filters, washs, the dry Co that gets
2+(EAA) salt.
(2) polyethylene of modified by maleic acid anhydride graft:
With the maleic anhydride of 2kg, the 100g dicumyl peroxide is dissolved in the 5L acetone, mixes with 100kg1F7B.
Drying removes solvent, adds in the forcing machine, extrudes under 190-210 ℃ of condition, and granulation gets the polyethylene of modified by maleic acid anhydride graft.
(3) preparation of modified starch master batch:
In twin screw extruder, locate to be metered into 80kg/h W-Gum (water-content 14%), the 1%NaOH solution of 20kg/h, 8kg/h dodecane enetutanedioic acid anhydride at first section.Then at the glycerine of the 6th joint barrel place's metering 5kg/hEAA10kg/h and the mixture of sorbyl alcohol (1: 1), 2kg/h oleic acid, 1kg/h glyceryl monostearate.Heating mixes, reaction, and vaccum dewatering is extruded, and granulation gets treated starch master batch water content less than 5%.Processing condition are:
Twin screw extruder L/D=48
150 rev/mins of rotating speeds
Temperature: 6 districts, 5 districts, 4 districts, 3 districts, 2 districts, 1 district
95℃ 120℃ 130℃ 140℃ 140℃ 120℃
Vacuum tightness:＜100mmHg
Require: between the moisture 4-5% of master batch, particle transparency height.
(4) preparation of reversible Degradable Starch Resin:
55 parts of modified starch master batches, 10 parts of EAA (5% acrylic acid content), 5 parts of maleic anhydride modified polyethylene, 6 parts on o-methoxybenzoic acid zinc, Fe
3+(EAA) 0.5 part, after 0.2 part of antioxidant 264,25 parts of LDPE mix, in twin screw extruder, extrude, granulation, vaccum dewatering obtains transparent even particle simultaneously.Processing condition are as follows:
Twin screw extruder L/D=44-48
300 rev/mins of rotating speeds
Moment of torsion 70-90%
Temperature: 1 district, 2 districts, 3 districts, 4 districts, 5 districts, 6 district's melts
105℃ 130℃ 170℃ 140℃ 170℃ 150℃ 150-160
Vacuum tightness:＜100mmHg
The gained particle is handled: little yellow, and translucent, homogeneous
Moisture content: 1-2%
Melt index: 2-4g/10min (160 ℃)
With resin blown film on general inflation film manufacturing machine, D=45mm
L/D=30 temperature: 1 district, 2 districts, 3 districts, 4 district's die heads
102℃ 135℃ 140℃ 160℃ 150℃
Mechanical property:
Tensile strength (indulging): 21.5MPa
(horizontal stroke): 18MPa
Elongation at break (indulging): 300MPa
(horizontal stroke): 450MPa
Degradation property: 400W UV-irradiation fragmentation in 48 hours
The compost experiment: 1 month, many apertures and micropopulation appearred in weightlessness 10%, 8 months weightlessness about 60%, and caudacoria fragmentation in 12 months, the overwhelming majority disappears.
Embodiment 2
65 parts of the modified starch master batches that makes by various and step identical in the example 2,7 parts of EAA (5% vinylformic acid), 5 parts on adjacent methylamino acid zinc, Fe
3+(EAA) 0.6 part, 0.2 part of antioxidant 264,8 parts of polyurethane termoplastic elastomers, LDPE (D=0.905g/cm
3, MI=3g/10min) 20 parts, after mixing, in twin screw extruder, extrude, granulation, vaccum dewatering gets translucent even particle simultaneously.The gained resin is blow molded into thin unconcerned; Its mechanical property is:
Tensile strength: (indulging): 19.2MPa
(horizontal stroke): 18.6MPa
Elongation at break: (indulging): 450%
(horizontal stroke): 420%
Degradation property: compost experiment weightless film rupture in 30%, 6 month in 2 months, completely dissolve in 18 months.
Embodiment 3.
80 parts of modified starch master batches, 5 parts of maleic anhydride modified resins, 10 parts in lime carbonate (containing lime carbonate 80%), 3 parts on o-methoxybenzoic acid zinc, 15 parts of polyurethane termoplastic elastomers are extruded in twin screw extruder, granulation, resin water content 5-6%.
Available injection moulding method is processed into various hard products, processing temperature 160-180 ℃, has rigidity and toughness preferably.Be pressed into the thick sheet material of 1mm, completely dissolve in 12 months under the compost state.
Claims (21)
1. reversible cross-linked starch resin compound is characterized in that forming and comprises:
(A) the modified starch master batch of 20-80 part,
(B) ethene one acrylic copolymer of 4-20 part,
(C) catalyzer of 1-4 branch,
(D) reversible cross-linking agent of 2-10 part,
(E) synthetic resins of 13-60 part, described synthetic resins are polyethylene, polypropylene, urethane resin, vibrin or their hydroxyls, carboxyl or aminoderivative,
Described (A) component modified starch master batch contains following composition:
A.70-90 Fen starch,
B.3-15 Fen active modifier, described active modifier are that Succinic anhydried derivative or molecular weight with chain alkyl are the maleic anhydride of 1000-5000,
C.2-5 Fen ethene one acrylic copolymer,
D.0.5-4 Fen alkaline additive,
E.2.5-15 Fen softening agent,
F.0.7-3 Fen flow ability modifying agent,
G.0.3-2 Fen dispersion agent,
H.3-8 Fen maleic anhydride grafted polyethylene modified resin,
Above-mentioned all umbers are parts by weight.
2. according to the described composition of claim 1, it is characterized in that the described starch of (A) component is W-Gum, potato starch, sweet potato starch, oxide ether starch, anionic starch or the etherification starch of water content below 14% (weight).
3. according to the described composition of claim 1, it is characterized in that the Succinic anhydried derivative with chain alkyl described in (A) component is octenyl Succinic anhydried, dodecenylsuccinic acid acid anhydride, hexadecylene base Succinic anhydried, octadecylene base Succinic anhydried.
4. according to the described composition of claim 1, it is characterized in that acrylic acid content in ethene one acrylic copolymer described in (A) component is more than 20% (weight).
5. according to the described composition of claim 1, it is characterized in that the softening agent described in (A) component is ethylene glycol, propylene glycol and their lower molecular weight condenses, glycerine or sorbyl alcohol.
6. according to the described composition of claim 1, it is characterized in that the described alkaline additive of (A) group is sodium hydroxide or potassium hydroxide.
7. according to the described composition of claim 1, it is characterized in that in (A) component, described flow ability modifying agent is glyceryl monostearate or oleic acid.
8. according to the described composition of claim 1, it is characterized in that the dispersion agent described in (A) component is or sorbitan mono-oleic acid ester.
9. according to the described composition of claim 1, it is characterized in that the maleic anhydride grafted polyethylene modified resin described in (A) combination is to be dissolved in the acetone with maleic anhydride and initiator mixing with polyethylene, in forcing machine, extrude, granulation makes.
10. according to the described composition of claim 1, it is characterized in that acrylic acid content is 5-15% (weight) in the described ethylene-acrylic acid copolymer of (B) component.
11. require 1 described composition according to profit, it is characterized in that the catalyzer of (C) component comprises Primary Catalysts, promotor and catalytic inhibitor.
12. require 11 described compositions according to profit only, it is characterized in that described Primary Catalysts is the transition metal salt of ethylene-acrylic acid.
13. according to the described line compound of claim 12, the transition metal salt that it is characterized in that described ethylene-acrylic acid is ethylene-acrylic acid molysite, cobalt salt or manganese salt.
14., it is characterized in that described promotor comprises the unsaturated compound of oleic acid, low molecular weight polybutadiene or styrene-butadiene block copolymer according to the described composition of claim 11.
15., it is characterized in that described catalytic inhibitor is an oxidation inhibitor according to the described composition of claim 11.
16. according to the described composition of claim 15, it is characterized in that described oxidation inhibitor is 2,6-di-tert-butyl methyl phenol or four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester.
17. according to the described composition of claim 11, the ratio that it is characterized in that described Primary Catalysts, promotor and catalytic inhibitor is 70-80: 20-30: 5-15 (ratio of weight and number).
18., it is characterized in that the described reversible cross-linking agent of component (D) is an o-methoxybenzoic acid zinc according to the described composition of claim 1.
19. the preparation method of any described reversible cross-linked starch resin compound in the claim 1-18 item may further comprise the steps:
(1) preparation of modified starch master batch:
Starch, properties-correcting agent, ethylene-acrylic acid copolymer, softening agent, flow ability modifying agent and alkaline additive are reacted in twin screw extruder in proportion, extrude, granulation and getting, order of addition(of ingredients) is for obtaining graft starch with starch, maleic anhydride grafted polyethylene modified resin and alkaline additive reaction earlier, second section feeding then, add rest materials, obtain having good thermoplastic modified starch master batch;
(2) preparation of polymer catalyst:
The ethylene-acrylic acid copolymer of high acrylic acid content is dissolved in the alkaline solution, stirs the salts solution that adds transition metal down, promptly have precipitation to separate out, reacted 2 hours down at 80 ℃, the washing drying son amount Primary Catalysts that secures satisfactory grades, its transport property is very little, and has the good mixing performance with synthetic resins; This Primary Catalysts and promotor, catalytic inhibitor are mixed in proportion;
(3) preparation of biodegradable starch-resin particle;
With the modified starch master batch, ethylene-acrylic acid copolymer, catalyzer, reversible cross-linking agent and synthetic resins mix in proportion back extruding pelletization in twin screw extruder, remove unnecessary moisture content simultaneously and obtain Degradable Starch Resin provided by the present invention.
20. in accordance with the method for claim 19, wherein, step (1) is that starch is joined in the twin screw extruder, with pump maleic anhydride grafted polyethylene modified resin, sodium hydroxide solution and active modifier are metered into respectively simultaneously, reacting by heating adds ethylene-acrylic acid copolymer, softening agent and flow ability modifying agent and dispersion agent at the forcing machine middle part again, and vacuum is removed moisture content, extrude, granulation gets the modified starch master batch.Processing conditions: temperature: 90-100 ℃/120-130 ℃/120-130 ℃/120-130 ℃/130-140 ℃/120-130 ℃, rotating speed 200-300rpm, starch master batch requires the transparency height, plasticizing evenly, between the water content 5-8% (weight).
21. in accordance with the method for claim 19, wherein step (3) processing temperature from feeding to die head 90-110 ℃/100-150 ℃/120-180 ℃/130-190 ℃/140-200 ℃/120-180 ℃, melt temperature 140-180 ℃.Melt moisture content 5-6% (weight), rotating speed 250-400rpm, moment of torsion 50-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96104665 CN1047783C (en) | 1996-04-17 | 1996-04-17 | Reversible cross-linked starch resin compound and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96104665 CN1047783C (en) | 1996-04-17 | 1996-04-17 | Reversible cross-linked starch resin compound and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1134433A CN1134433A (en) | 1996-10-30 |
| CN1047783C true CN1047783C (en) | 1999-12-29 |
Family
ID=5118432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96104665 Expired - Fee Related CN1047783C (en) | 1996-04-17 | 1996-04-17 | Reversible cross-linked starch resin compound and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1047783C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2740755A1 (en) | 2012-12-07 | 2014-06-11 | Fonds de l'ESPCI - Georges Charpak | Processable semi-crystalline polymer networks |
| CN103724674B (en) * | 2013-12-30 | 2015-09-09 | 成都新柯力化工科技有限公司 | Transparent filling master batch of a kind of starch and preparation method thereof |
| CN106117982A (en) * | 2016-06-27 | 2016-11-16 | 梅庆波 | A kind of preparation method of hydrophilic polyester master batch |
| CN109021298A (en) * | 2017-06-08 | 2018-12-18 | 吉林农业大学 | A kind of take basic amino acid as the edible starch film of double positive polarity crosslinking agents |
| JP2022150037A (en) | 2021-03-25 | 2022-10-07 | 富士フイルムビジネスイノベーション株式会社 | Resin particle |
| CN116904004B (en) * | 2023-09-13 | 2023-11-14 | 泰州泽钰新材料科技有限公司 | Degradable starch crosslinked particle modified PBAT polyester master batch and preparation process thereof |
-
1996
- 1996-04-17 CN CN 96104665 patent/CN1047783C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1134433A (en) | 1996-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1058736C (en) | Preparing method for biodegradation compound and its use | |
| US7608649B2 (en) | Biodegradable materials from starch-grafted polymers | |
| CN103992517B (en) | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof | |
| KR20170075052A (en) | Resin composition for mulching film and biodegradable mulching film using the same | |
| CN113248798B (en) | starch/cellulose/PBAT composite film and preparation method thereof | |
| CN101591467A (en) | A kind of polylactic wood/plastic composite material and preparation method thereof | |
| JP2003073539A (en) | Highly strong biodegradable resin composition and molded article | |
| CN113637299B (en) | Heat-resistant and impact-resistant polylactic acid composite material and preparation method and application thereof | |
| CN112358708A (en) | Biodegradable film blowing modified material with high starch content and preparation method thereof | |
| CN1583851A (en) | Hydrophobic completely biological degradable materials and preparing method thereof | |
| CN1047783C (en) | Reversible cross-linked starch resin compound and its preparation method | |
| JP2003055470A (en) | Biodegradable resin composition | |
| CN115418083A (en) | Low-cost PBAT biodegradable material for film bag and preparation method thereof | |
| CN102134380A (en) | Completely biodegradable composite material and preparation method thereof | |
| CN112405931B (en) | Preparation method of nano-montmorillonite reinforced starch-based biodegradable blown film material, product and application thereof | |
| CN1622970A (en) | Biodegradable resin composition and manufacturing method thereof | |
| JP2017533984A (en) | Concentrate composition for polymer chain extension | |
| CN107488298A (en) | A kind of bio-based complete degradable plastic masterbatch, its preparation method and application | |
| CN1712436A (en) | Aliphatic polyester/starch/clay ternary degradable resin and production thereof | |
| CN113912989A (en) | Novel biodegradable tackifying master batch and preparation method thereof | |
| CN112662144A (en) | Preparation method of plastic particles beneficial to degradation | |
| KR100332163B1 (en) | Biodegradable resin composition and a method for preparation thereof | |
| CN111286164B (en) | Biodegradable plastic and preparation method thereof | |
| CN110054872B (en) | PET/PE blending alloy and preparation method and application thereof | |
| CN110734631B (en) | Lignin-based biodegradable polybutylene succinate film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |