CN1267681A - Degradeable resin composition and its preparation and application - Google Patents
Degradeable resin composition and its preparation and application Download PDFInfo
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Abstract
The degradeable resin composite consists of (in weight portions): synthesized resin 20-85, supplementary material 0-20 and degradeable resin composite mother grain 15-85 and the degradeable resin composite mother grain contains photosensitive agent, degradation promoter, modifier, biological degradation primer,plasticizer, water, oxidant, free radical primer, photosensitive promoter, biological degradation promoter, degradation controlling agent and synthesized resin. The synergic effect of the components of degradable resin composite capable of producing self-oxidation degradation, free radical initiated degradation, light degradation, water degradation and biological degradation makes the resin composite degradable into non-toxic CO2 and water.
Description
The present invention relates to the degradative resin technical field, refer in particular to a kind of degradable resin composition and manufacture method thereof and application.
As everyone knows, the waste of synthetic resin article has become one of topmost public hazards of current society to " white pollution " that physical environment caused, and administering " white pollution " has become the problem that countries in the world are all paid close attention to.The scientist of various countries explores through long-term, has proposed the various schemes that address this problem, and is wherein, feasible, also have most the scheme of development potentiality to be: as to replace existing resin with the resin that can degrade.
Make a general survey of the technical scheme of various degradative resins, mainly contain following four kinds: photodegradation resin, Biodegradable resin, photo ﹠ bio degradable resin and water degradative resin.
First kind, the photodegradation resin, be that effect by natural light is progressively ruptured the long-chain of synthetic resins, USP.4, propose in 121,025 (1978) patents to use the cerium stearate of 0.05-0.5% can make the polyethylene photodegradation, its major defect is that manufacturing cost is higher, and still remaining bigger relic after the degraded can not thoroughly be degraded to nontoxic carbonic acid gas and water.
Second kind, Biodegradable resin, as USP.4, propose to utilize microorganism to make carbohydrate fermentation such as glucose in 393,167 and extract, make microorganism synthetic Biodegradable resin, can successfully realize biological degradation, but this resinoid thermostability is bad, the fragility height, difficulty of processing is bigger, and the cost costliness.
The third is the photo ﹠ bio degradable resin, proposes in Chinese patent CN1173515A, with common synthetic resins, treated starch, aliphatic polyester, organo-peroxide, the blend of photoxidation promotor.The advantage of this type of degradative resin is that technology is simpler, and cost is close with common synthetic resins, but can't resolve the relatively poor problem of consistency between starch and the synthetic resins, and processing characteristics is undesirable, also can not thoroughly be degraded to nontoxic carbonic acid gas and water.
The 4th kind, the water degradative resin, at USP.3, proposed a kind of aqueous solution that contains polyvinyl alcohol, starch and tensio-active agent by curtain coating in 316,190 and produced nonadherent water degradative membrane, this resinoid is met water can be dissolved, it is attended by biological degradation toward contact and takes place in the water degradation process, this resinoid is difficult for processing, and range of application is minimum, and physical and mechanical properties is relatively poor.
The object of the present invention is to provide a kind of degradable resin composition and manufacture method thereof and application, this degradable resin composition has comprised the degraded of produced autoxidation, free radical triggered degradation, photodegradation, water degraded and the biodegradable degradable resin composition master batch of suitable proportion, it can make product abandonment thing that this degradable resin composition the makes synergy because of multiple degraded composition, reach the purpose that thoroughly is degraded to carbonic acid gas and water, and reach purpose with low cost, that physical and mechanical properties good, technology is simple and easy to process simultaneously.
The object of the present invention is achieved like this: a kind of degradable resin composition is characterized in that this degradable resin composition forms (parts by weight) by following composition and proportioning:
Synthetic resins 20-85
Auxiliary material 0-20
Degradable resin composition master batch 15-80
Wherein this degradable resin composition master batch contains following composition and proportioning:
Photosensitizers 0.0067-0.625
Short degradation agents 50-90
Properties-correcting agent 1.3-3.75
Biological degradation initiator 6.7-18.8
Softening agent 0.67-2.25
Water 2-3.5
Autoxidator 0.067-1
Radical initiator 0.013-0.025
Photosensitive accelerant 0.067-2.5
Biodegradation promotor 0.17-1.25
Degraded control agent 0.0067-1.25
Synthetic resins 1-20
This synthetic resins comprises at least a in polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymeric amide, polycarbonate, the polyterephthalate; This auxiliary material comprises linking agent, whipping agent, Masterbatch, pigment, spices; This photosensitizers comprises at least a in acetylacetonate cobalt and the following composition: the metallic compound of methyl ethyl diketone or its metal complex, dithiocar-bamate complex compound, two seleno carboxylamine salt complexs, benzophenone and derivative, quinone, ferrocene and derivative thereof, halogen compounds, transition metal oxide; Should comprise lime carbonate and/or the former powder of agalmatolite by short degradation agents; This properties-correcting agent comprises that density is 0.85-0.90g/cm
3Ultra-low density polyethylene; This biological degradation initiator comprises the derivatived cellulose of polyvinyl alcohol and/or substitution value≤2; This softening agent comprises at least a in glycerine, alkyl alcohol, vegetables oil, the ester; This autoxidator comprises organic acid or tartaric acid; This radical initiator comprises peralcohol or azo-compound; This photosensitive accelerant comprises stearate; , this biodegradation promotor comprises at least a among poly butyric ester and derivative thereof, polycaprolactone, hydrophobic protein, poly(lactic acid), sodium alginate, pectin, agar, Tri sodium Phosphate, trisodium phosphate, dimethylamine, the gelatin, Lao Starters; This degraded control agent comprises at least a in salicylate and derivative, benzophenone and derivative thereof, benzotriazole and derivative thereof, triazine and derivative thereof, organic nickel complex compound, phenol, amine, monothioester, phosphorous acid ester, the inorganic or pigment dyestuff.
This manufacture method comprises the steps:
(1) select following composition and proportioning (parts by weight):
Synthetic resins 20-85
Auxiliary material 0-20
Degradable resin composition master batch 15-80
Wherein this degradable resin composition master batch contains following composition and proportioning:
Photosensitizers 0.0067-0.625
Short degradation agents 50-90
Properties-correcting agent 1.3-3.75
Biological degradation initiator 6.7-18.8
Softening agent 0.67-2.25
Water 2-3.5
Autoxidator 0.067-1
Radical initiator 0.013-0.025
Photosensitive accelerant 0.067-2.5
Biodegradation promotor 0.17-1.25
Degraded control agent 0.0067-1.25
Synthetic resins 1-20
(2) make the degradable resin composition master batch by following step:
(1) photosensitizers, short degradation agents, properties-correcting agent are joined in the high-speed mixer uniform mixing;
(2) biological degradation initiator, softening agent and water are joined extruding pelletization in the screw extrusion press;
(3) mixture of preparation in (1), particle and autoxidator, radical initiator, photosensitive accelerant, biodegradation promotor, degraded control agent and the synthetic resins of (2) middle preparation are joined in the low speed mixer, uniform mixing, use the screw extrusion press granulation, make the degradable resin composition master batch.
(3) be mixed:
Synthetic resins 20-85, auxiliary material 0-20 and degradable resin composition master batch 15-80 are mixed evenly, make degradable resin composition of the present invention; Degradable resin composition is applicable to the goods of manufacturing extrusion moulding, injection moulding, slush molding, calendering formation, blow molding, foaming.
Major advantage of the present invention is:
1, comprised in the degradable resin composition master batch of the present invention and can produce autoxidation degraded, free radical triggered degradation, photodegradation, water degraded and biodegradable composition, the synergy of its multiple degraded composition, strengthened the degraded effect greatly, the product abandonment thing that degradable resin composition of the present invention is made can thoroughly be degraded to carbonic acid gas without any side effects and water, has solved " white pollution " problem that influences to environment.
2, manufacture method of the present invention is very simple, only needs the forcing machine granulation, does not need special equipment, and raw material cheaply is easy to get, and is with a wide range of applications.
3, degradable resin composition of the present invention is applicable to and manufactures extrusion moulding, injection moulding, slush molding, calendering formation, the goods of type such as blow molding, foaming, can be according to the needs that use, adjust the proportioning of degradable resin composition master batch, for example manufacture disposable mulch film or packaging film, can increase the consumption of master batch, make its degraded rapidly after use; And manufacture repeatedly or goods that the long period uses, then can reduce the consumption of this master batch relatively, make it in the usage period, keep stablizing.
4, the physical and mechanical properties of degradable resin composition of the present invention is good, is easy to processing, can be processed into goods according to the complete processing of common synthetic resins, need not to carry out any change.
5, the cost of degradable resin composition of the present invention is lower than common synthetic resins.
The present invention is further described below in conjunction with preferred embodiment and accompanying drawing.
The film degradation graphic representation that Fig. 1 makes for degradable resin composition of the present invention.
Embodiment 1
The composition of degradable resin composition of the present invention and proportioning (kilogram):
Ldpe resin 168
Degradable resin composition master batch 100
This degradable resin composition master batch contains following composition and proportioning:
Photosensitizers: acetylacetonate cobalt 0.02
Diacetylmethane iron 0.006
Iron(ic) chloride 0.43
Short degradation agents: lime carbonate 55
The former powder 25 of agalmatolite
Properties-correcting agent: ultra-low density polyethylene 1.6
Biological degradation initiator: polyvinyl alcohol 10
Softening agent: glycerine 1
Water 2.6
Autoxidator: oleic acid 0.1
Radical initiator: dibenzoyl peroxide 0.014
Photosensitive accelerant: Zinic stearas 0.5
Biodegradation promotor: polycaprolactone 0.08
Sodium alginate 0.06
Lao Starters 0.04
Degraded control agent: Whitfield's ointment (4-tertiary butyl phenyl ester) 0.1
Octabenzone 0.05
Synthetic to fat: new LDPE (film grade) 3.4
Wherein photosensitizers can produce synergistic diacetylmethane iron and iron(ic) chloride for the acetylacetonate cobalt and with it, has good photosensitive effect and the relatively low effect of cost.
Short degradation agents wherein is lime carbonate and the former powder of agalmatolite, and the former powder of lime carbonate and agalmatolite is taken as common fillers usually and uses, and has ignored it to the oxygen uptake of synthetic resins, the influence of oxygen permeability.The inventor finds through experiment: add oxygen uptake, oxygen permeability that lime carbonate and the former powder of agalmatolite can increase goods significantly in synthetic resins.Experiment shows, when 100 parts of linear low density polyethylenes, and 35 parts of ethylene-propylene copolymers, 120 parts of lime carbonate after 60 parts of former powder of agalmatolite and 1.5 parts of oleic acid mix, are blow molded into film, and its oxygen permeability is 10.3L/atm.m
2And the oxygen permeability of pure linear low-density polyethylene film only is 4L/atm.m .24h,
2.24h.The oxygen uptake of goods, the increase of oxygen permeability is to promoting its oxidative degradation and biological degradation significant, the oxygen uptake of goods, oxygen permeability increases, just increased in the goods, the touch opportunity of outside and oxygen, in goods, the outside has formed one to oxidative degradation and the very favourable oxygen-enriched environment of biological degradation, promoted the generation of more superoxide and free radical greatly, promoted the generation of a large amount of oxygen enrichment hydrophilic compounds, increased the chance of microbial attack, for microbiological deterioration provides abundant oxygen, therefore oxidative degradation and biological degradation will have been strengthened inevitably greatly, and speed has also been accelerated greatly.Experimental results show that: the amount of filling of lime carbonate and the former powder of agalmatolite is big more, and then the degradation speed of goods is also just fast more.Because the cost of lime carbonate and the former powder of agalmatolite is very cheap, cost well below common synthetic resins, and its addition is bigger, so the cost of the degradable resin composition goods described in the present invention is cheaper than common synthetic resins, thereby is easy to be widely used.
Properties-correcting agent wherein is ultra-low density polyethylene, and density is 0.85-0.90g/cm
3The adding ultra-low density polyethylene is consistency and the avidity in order to improve inorganic additives and synthetic resins among the present invention.The ultra-low density polyethylene resin has long molecular chain, branching content is few, degree of crystallinity is low, mobile very good, with after inorganic compound mixes, can be coated on the inorganic additives surface equably, on the interface of inorganic additives, form one deck ductile bed, lax and reduced interfacial stress, this ultra-low density polyethylene is more far better than general synthetic resins with the affinity of inorganic additives.It is also all fine with the consistency of general synthetic resins.Experimental results show that: add this ultra-low density polyethylene as properties-correcting agent, can make the physical and mechanical properties of goods and processing characteristics reach gratifying effect.
Biological degradation initiator wherein is a polyvinyl alcohol.In the product degradation process, it can absorb extraneous moisture content, make the product surface swelling, simultaneously, the water degraded also takes place himself, because by plasticising effectively, so the common synthetic resins in it and the goods has good consistency, the forcing machine by High Temperature High Pressure and high shear force in preparation process has made the combination that has produced mutual winding and part chemical bond between these two kinds of polymers in the process of preparing product for it.Because biological degradation initiator generation hydrolysis, thus make its with common synthetic resins polymer between mutual winding and the part chemical bond to combine state destroyed, therefore the synthetic resins macromolecular chain has also caused partly and has ruptured.After having spent stationary phase in the product degradation process, because at autoxidator, radical initiator, photosensitizers, under the effect of photosensitive accelerant and short degradation agents, synthetic macromolecule in the goods is by a large amount of chain ruptures, a large amount of lower molecular weight oxygen enrichment hydrophilic compounds have been formed, and product surface has been wet fully under the multiple action of biological degradation initiator, the content of lower molecular weight oxygen enrichment hydrophilic compounds has sharply increased, so the condition of microbial attack macromolecular material has been satisfied fully, so speck is born with and is attached to its surface at an easy rate, a large amount of lower molecular weight oxygen enrichment hydrophilic compounds have been decomposed soon, from then on biological degradation just has been initiated, and continues to go on.
Softening agent wherein is a glycerine, and it mainly acts on is to carry out modification to giving birth to the degraded initiator, makes itself and common synthetic resins have good consistency and is easy to thermoplasticity and process, and simultaneously, himself also has good degradation property, can play the effect that promotes degraded.
Water wherein has two effects, and the first is carried out modification with softening agent to the biological degradation initiator, and it two is water degraded and the biological degradations that promote goods.
Autoxidator wherein is an oleic acid, it can autoxidation produce superoxide in physical environment, this superoxide can decomposite free radical under illumination, cause synthetic resins polymer long-chain fracture degraded, its can also with the transition metal complexing in the soil, the high molecular synthetic resin autoxidation in the catalysis goods.
Radical initiator wherein is a dibenzoyl peroxide, and because of containing weak bond " O-O-" in the molecule, it is good for can be lower, only be 20-30 kilocalorie/mol, under natural light irradiation, be easy to produce the weak bond fracture, generate free radical, cause high-polymer molecular long-chain fracture degraded.
Photosensitive accelerant wherein is a Zinic stearas, has the photodegradative effect of synthetic resins that promotes in the goods, also has effect lubricated and increase mixing effect.
Biodegradation promotor wherein is polycaprolactone, sodium alginate and junket, and biological degradation can take place for himself, cooperates the biological degradation initiator can quicken, continue the biodegradable process of expansion, promotes biodegradable effect effectively thereby play.
Degraded control agent wherein is Whitfield's ointment (4-tertiary butyl phenyl ester) and Octabenzone, it can suppress the destruction of ultraviolet ray to synthetic resins effectively, delay the degradation time of synthetic resins, make goods that be arranged a metastable period in physical environment, keep goods stability in use, to the goods that the need long period uses, even more important.
Degradable resin composition of the present invention is in a word realized degrading by multiple degraded modes such as autoxidation degraded, free radical triggered degradation, photodegradation, water degraded and biological degradations, and wherein various degraded modes are polynary combinations, supplement and complement each other, and are synergistic.Degradable resin composition goods of the present invention have been spent stationary phase in physical environment after, the autoxidation degraded has taken place rapidly, free radical triggered degradation and photodegradation reaction, the result of reaction is the synthetic macromolecule splitting of chain in the goods, a large amount of lower molecular weight oxygen enrichment hydrophilic compounds have been formed, the internal structure of goods is more lax greatly than originally, at this moment, biological degradation initiator in the goods just can absorb extraneous moisture content more fully, thereby caused the product surface swelling, has wettability, the water degraded has taken place, the result is that product surface has wettability and generated the lower molecular weight oxygen enrichment hydrophilic compounds that is easy in a large number by microbial metabolism, along with a large amount of lower molecular weight oxygen enrichment hydrophilic compounds are fallen by microbiological degradation, biological degradation just has been initiated, the concentration of other DeR product has also decreased, and the autoxidation degraded, the free radical triggered degradation, photodegradation and water DeR then will go on continuously in order to continue to reach the concentration balance of reaction product.New active compound that produces after the biological degradation such as heterocycle molecule etc. can absorb outside energy, and the free radical activation energy that produces in other several degradation processes is reduced; And the energy that discharges during biological degradation can help other DeR to overcome the activation energy energy barrier and acceleration.Multiple degraded mode come to this polynary combination, synergy, continue to carry out, product degradation is CO the most at last
2And H
2O.
The manufacture method of degradable resin composition of the present invention must adopt the mixed and modified and mixing method of substep, just can make between each composition of degradable resin composition to have preferable consistency, makes goods be easy to thermoplasticity processing, and its concrete steps are as follows:
(1) selects raw material by above-mentioned composition and proportioning: no longer repeat.
(2) make the degradable resin composition master batch by following step: (1) joins photosensitizers, short degradation agents and properties-correcting agent in the high-speed mixer and mixes, and purpose is consistency, avidity and dispersing uniformity between increasing mutually.(2) biological degradation initiator, softening agent and water are joined granulation in the screw extrusion press, its purpose is for to carry out modification to the biological degradation initiator, improves the consistency of itself and synthetic resins and makes it be easy to thermoplasticity processing.(3) mixture of preparation in above-mentioned (1) and (2) and particle and all the other each compositions are put into low speed mixer and mix, use the screw extrusion press granulation, make the about double centner of degradable resin composition master batch of the present invention.
(3) be mixed:
With the degradable resin composition mother who makes among 168 kilograms of ldpe resins and above-mentioned (two)
The grain double centner mixes, and makes degradable resin composition of the present invention.
The application of degradable resin composition of the present invention:
Degradable resin composition of the present invention is blow molded into the agricultural mulching of 0.008mm and 0.012mm, measures its physical and mechanical properties index and see Table one and table two:
Table one: the physical and mechanical properties index of degradable resin composition mulch film of the present invention
(thickness 0.008mm)
| Sequence number | Interventions Requested | Unit | Technical requirements | Assay |
| ??1 | Tensile loading is indulged/horizontal stroke | ????N | ??≥1.6 | ??3.3/3.0 |
| ??2 | Elongation at break is indulged/horizontal stroke | ????％ | ??≥160 | ??510/835 |
| ??3 | The right-angle tearing load is indulged/horizontal stroke | ????N | ??≥0.6 | ??1.0/1.2 |
| Remarks | Technological standard is a GB13735-921V class index | |||
Table one: the physical and mechanical properties index of degradable resin composition mulch film of the present invention
(thickness 0.012mm)
| Sequence number | Interventions Requested | Unit | Technical requirements | Assay |
| ??1 | Tensile loading is indulged/horizontal stroke | ???N | ???≥1.6 | ???3.9/2.9 |
| ??2 | Elongation at break is indulged/horizontal stroke | ???％ | ???≥160 | ???530/856 |
| ??3 | The right-angle tearing load is indulged/horizontal stroke | ???N | ???≥0.6 | ???1.3/1.5 |
| Remarks | Technological standard is a GB13735-921V class index | |||
Prove from table one and table two: the mulch film that is blow molded into degradable resin composition of the present invention has the better physical mechanical property.
The degradation property experiment of above-mentioned agricultural mulching:
Above-mentioned two kinds of mulch films are taped against carry out practical application in the farmland.Sight is looked into the degraded variation of mulch film and is consulted Fig. 1, and two kinds of mulch films begin obvious degradation after 90 days, and mulch film is cleaved into big and small sheet; After 180 days, become tiny sheet, drawing with have gentle hands light one is fragmentation, if twist with the fingers with hand rubbing, i.e. and pulverize powder; After 280 days, film has all disappeared.From degradation effect, the degraded of two kinds of degradative membranes is more satisfactory, and its degradation curve as shown in Figure 1.
Find out significantly that from Fig. 1 the agricultural mulching that degradable resin composition of the present invention is made in 280 days time, is degraded to CO fully
2And H
2O.
Soil water loss amount and the experiment of soil moisture conservation effect behind the above-mentioned agricultural mulching overlay film:
Use simultaneously with above-mentioned two kinds of agricultural mulchings and common polythene mulch film, survey its soil water loss amount and soil moisture conservation value, the results are shown in Table three:
Table three: soil water loss amount and soil moisture conservation value behind the overlay film
| Film kind project | Soil water loss amount (g/m behind the overlay film 2. day) | Soil moisture conservation value (g/m 2. day) |
| 0.008mm mulch film of the present invention | ?????????21.35 | ??????776.85 |
| 0.012mm mulch film of the present invention | ?????????19.92 | ??????781.67 |
| The common polythene mulch film | ?????????18.23 | ??????790.32 |
Experimental result shows: use the mulch film of degradable resin composition blowing of the present invention, its soil water loss amount, soil moisture conservation value and common polythene mulch film basically identical.
Experimental example 2
The composition of degradable resin composition of the present invention and proportioning (kilogram):
High-density polyethylene resin 257
Linking agent: iso-cyanuric acid triallyl ester 4
Degradable resin composition master batch 100
This degradable resin composition master batch contains following composition and proportioning:
Photosensitizers: acetylacetonate cobalt 0.015
Dithiocarbamic acid iron 0.005
Acetylacetonate iron 0.551
Short degradation agents: lime carbonate 53
The former powder 22 of agalmatolite
Properties-correcting agent: ultra-low density polyethylene 2
Biological degradation initiator: Mierocrystalline cellulose diethyl ether 11
Softening agent: ethylene glycol 1.3
Water 2.8
Autoxidator: palmitinic acid 0.1
Radical initiator: azobisisobutyronitrile 0.019
Photosensitive accelerant: iron stearate 0.3
Biodegradation promotor: poly--3-hydroxybutyric acid-3 hydroxyl valerate 0.08
Agar 0.05
Gelatin 0.05
Degraded control agent: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole 0.08
Oxamide 0.05
Synthetic resins: high density polyethylene(HDPE) 6
Polyvinyl chloride 0.6 its manufacture method is identical with enforcement 1, so do not repeat.Above-mentioned degradable resin composition can be made required goods with extrusion moulding or slush molding.The composition of embodiment 3 degradable resin compositions of the present invention and proportioning (kilogram): polystyrene 300 whipping agents: Cellmic C 121 10 degradable resin composition master batches 100 these degradable resin composition master batches contain following composition and proportioning: photosensitizers: acetylacetonate cobalt 0.02
Two seleno carboxylamine nickel 0.006
Benzophenone 0.213 short degradation agents: lime carbonate 54
Former powder 23 modifier of pyrophillite: ultra-low density polyethylene 1.3 Initiation of biodegradation agent: cellulose diacetate 12 plasticizer: soybean oil 1.4 water 3 autoxidators: citric acid 0.12 radical initiator: dibenzoyl peroxide 0.016 photosensitive accelerant: cerium stearate 0.5 biodegradation promotor: PLA 0.08
Sodium alginate 0.06
Dimethylamine 0.04 degraded control agent: 2,4,6-three (2 ', 4 '-dihydroxy phenyl)-1,3,5-triazine 0.032,2 '-thiobis (4-tert-octyl phenol) nickel, 0.015 synthetic resins: polystyrene 4
Polycarbonate 0.2 its manufacture method is identical with embodiment 1, so do not repeat.Above-mentioned degradable resin composition can be made snack container with foaming and use.The composition of embodiment 4 degradable resin compositions of the present invention and proportioning (kilogram): acrylic resin 67 white master batch 3 degradable resin composition master batches 100 these degradable resin composition master batches contain following composition and proportioning: photosensitizers: acetylacetonate cobalt 0.03
Anthraquinone 0.007
Ferrocene 0.245 short degradation agents: lime carbonate 53
Former powder 24 modifier of pyrophillite: ultra-low density polyethylene 1 Initiation of biodegradation agent: polyvinyl alcohol 15 plasticizer: ATBC 1.6 water 3.2 autoxidators: laurate 0.1 radical initiator: dicumyl peroxide 0.02 photosensitive accelerant: zinc stearate 0.5 biodegradation promotor: zeins 0.08
Agar 0.06
Tri sodium Phosphate 0.04 degraded control agent: 2,4,6-tri-butyl-phenol 0.01
Titanium dioxide 0.008
Synthetic resins: polypropylene 0.9
Polyethylene terephthalate 0.1
Polymeric amide 0.1
Its manufacture method is with embodiment 1, so do not repeat.
With above-mentioned degradable resin composition injection molding process, be processed into injection moulded products such as disposable cutter, fork, spoon.Have better machining property, the waste of its goods can be biodegradable into CO2 and H2O.
Embodiment 5
The composition of degradable resin composition of the present invention and proportioning (kilogram)
New LDPE (film grade) 335
Spices: 3-methoxyl group-4-hydroxy benzaldehyde 0.4
Degradable resin composition master batch 100
The composition and the proportioning of this degradable resin composition master batch are as follows:
Photosensitizers: acetylacetonate cobalt 0.02
N-halogen-succimide 0.006
Ferric oxide 0.164
Short degradation agents: lime carbonate 53
The former powder 25 of agalmatolite
Properties-correcting agent: ultra-low density polyethylene 1.8
Biological degradation initiator: polyvinyl alcohol 10
Softening agent: glycol ether 1
Water 2.6
Autoxidator: palmitinic acid 0.1
Radical initiator: Diisopropyl azodicarboxylate 0.02
Photosensitive accelerant: iron stearate 0.5
Biodegradation promotor: polycaprolactone 0.08
Pectin 0.04
Trisodium phosphate 0.04
Degraded control agent: Tyox B 0.02
Triphenyl phosphite 0.01
Synthetic resins: new LDPE (film grade) 5.6
Its manufacture method is with embodiment 1, so do not repeat.
Above-mentioned degradable resin composition is made sheet material with the calendering formation method, and the last degradable of its waste is CO
2And H
2O.
Claims (15)
1, a kind of degradable resin composition is characterized in that this degradable resin composition forms (parts by weight) by following composition and proportioning:
Synthetic resins 20-85
Auxiliary material 0-20
Degradable resin composition master batch 15-80
Wherein this degradable resin composition master batch contains following composition and proportioning:
Photosensitizers 0.0067-0.625
Short degradation agents 50-90
Properties-correcting agent 1.3-3.75
Biological degradation initiator 6.7-18.8
Softening agent 0.67-2.25
Water 2-3.5
Autoxidator 0.067-1
Radical initiator 0.013-0.025
Photosensitive accelerant 0.067-2.5
Biodegradation promotor 0.17-1.25
Degraded control agent 0.0067-1.25
Synthetic resins 1-20
2, degradable resin composition as claimed in claim 1 is characterized in that, this synthetic resins comprises at least a in polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymeric amide, polycarbonate, the polyterephthalate.
3, degradable resin composition as claimed in claim 1 is characterized in that, this auxiliary material comprises linking agent, whipping agent, Masterbatch, pigment, spices.
4, degradable resin composition as claimed in claim 1, it is characterized in that this photosensitizers comprises at least a in acetylacetonate cobalt and the following composition: the metallic compound of methyl ethyl diketone or its metal complex, dithiocar-bamate complex compound, two seleno carboxylamine salt complexs, benzophenone and derivative, quinone, ferrocene and derivative thereof, halogen compounds, transition metal oxide.
5, degradable resin composition as claimed in claim 1 is characterized in that, this short degradation agents comprises lime carbonate and/or the former powder of agalmatolite.
6, degradable resin composition as claimed in claim 1 is characterized in that, this properties-correcting agent comprises that density is 0.85-0.90g/cm
3Ultra-low density polyethylene.
7, degradable resin composition as claimed in claim 1 is characterized in that, this biological degradation initiator comprises the derivatived cellulose of polyvinyl alcohol and/or substitution value≤2.
8, degradable resin composition as claimed in claim 1 is characterized in that, this softening agent comprises at least a in glycerine, alkyl alcohol, vegetables oil, the ester.
9, degradable resin composition as claimed in claim 1 is characterized in that, this autoxidator comprises organic acid or tartaric acid.
10, degradable resin composition as claimed in claim 1 is characterized in that, this radical initiator comprises peralcohol or azo-compound.
11, degradable resin composition as claimed in claim 1 is characterized in that, this photosensitive accelerant comprises stearate.
12, degradable resin composition as claimed in claim 1, it is characterized in that this biodegradation promotor comprises at least a among poly butyric ester and derivative thereof, polycaprolactone, hydrophobic protein, poly(lactic acid), sodium alginate, pectin, agar, Tri sodium Phosphate, trisodium phosphate, dimethylamine, the gelatin, Lao Starters.
13, degradable resin composition as claimed in claim 1 is characterized in that: this degraded control agent comprises at least a in salicylate and derivative, benzophenone and derivative thereof, benzotriazole and derivative thereof, triazine and derivative thereof, organic nickel complex compound, phenol, amine, monothioester, phosphorous acid ester, the inorganic or pigment dyestuff.
14, a kind of manufacture method of degradable resin composition is characterized in that this manufacture method comprises the steps:
(1) select following composition and proportioning (parts by weight):
Synthetic resins 20-85
Auxiliary material 0-20
Degradable resin composition master batch 15-80
Wherein this degradable resin composition master batch contains following composition and proportioning:
Photosensitizers 0.0067-0.625
Short degradation agents 50-90
Properties-correcting agent 1.3-3.75
Biological degradation initiator 6.7-18.8
Softening agent 0.67-2.25
Water 2-3.5
Autoxidator 0.067-1
Radical initiator 0.013-0.025
Photosensitive accelerant 0.067-2.5
Biodegradation promotor 0.17-1.25
Degraded control agent 0.0067-1.25
Synthetic resins 1-20
(2) make the degradable resin composition master batch by following step:
(1) photosensitizers, short degradation agents, properties-correcting agent are joined in the high-speed mixer uniform mixing;
(2) biological degradation initiator, softening agent and water are joined extruding pelletization in the screw extrusion press;
(3) mixture of preparation in (1), particle and autoxidator, radical initiator, photosensitive accelerant, biodegradation promotor, degraded control agent and the synthetic resins of (2) middle preparation are joined in the low speed mixer, uniform mixing, use the screw extrusion press granulation, make the degradable resin composition master batch.
(3) be mixed:
Synthetic resins 20-85, auxiliary material 0-20 and degradable resin composition master batch 15-80 are mixed evenly, make degradable resin composition of the present invention.
15, a kind of application of degradable resin composition is characterized in that this degradable resin composition is applicable to the goods of manufacturing extrusion moulding, injection moulding, slush molding, calendering formation, blow molding, foaming.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99103064A CN1129638C (en) | 1999-03-19 | 1999-03-19 | Degradeable resin composition and its preparation and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99103064A CN1129638C (en) | 1999-03-19 | 1999-03-19 | Degradeable resin composition and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
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| CN1267681A true CN1267681A (en) | 2000-09-27 |
| CN1129638C CN1129638C (en) | 2003-12-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99103064A Expired - Fee Related CN1129638C (en) | 1999-03-19 | 1999-03-19 | Degradeable resin composition and its preparation and application |
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