CN105482093A - Carbon dioxide-propylene oxide modified copolymer, preparation method thereof and carbon dioxide based biodegradable mulch film - Google Patents
Carbon dioxide-propylene oxide modified copolymer, preparation method thereof and carbon dioxide based biodegradable mulch film Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08L2201/06—Biodegradable
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- 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
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Abstract
The invention belongs to the field of film materials and particularly relates to a carbon dioxide-propylene oxide modified copolymer, a preparation method thereof and a carbon dioxide based biodegradable mulch film. The biodegradable mulch film is prepared from following raw materials: a carbon dioxide-propylene oxide copolymer and the carbon dioxide-propylene oxide modified copolymer, wherein the carbon dioxide-propylene oxide modified copolymer comprises a repeat unit with a structure shown in a formula (I) and a repeat unit with a structure shown in a formula (II). According to the biodegradable mulch film, the carbon dioxide-propylene oxide modified copolymer is added in a preparation process of the biodegradable mulch film, and the service life of the mulch film is prolonged through the synergistic effect of the carbon dioxide-propylene oxide modified copolymer and other raw materials. Experiment results show that the service life of the biodegradable mulch film can be 70-90 days, and the biodegradable mulch film beyond the service life can be degraded rapidly and completely.
Description
Technical field
The invention belongs to field of membrane material, particularly relate to a kind of carbon dioxide-epoxy propane modified copolymer and preparation method thereof and carbon dioxide-base Biodegradable mulch.
Background technology
Agricultural mulching can not only improve the soil moisture, keeps soil moisture, maintains Soil structure, and can play insect protected weeding, improves the effect of output of farm crop, is the requisite critical material of modern agriculture, is once considered to agriculture White Revolution.
Current China agricultural mulching area coverage has reached 3.8 hundred million mu, and consumption, up to 1,300,000 tons, has made tremendous contribution for solving China's foodgrain self-sufficiency and vegetable supply.But now China's film material is based on linear low density polyethylene, because mulch film general thickness is 4-8 μm, this ultra-thin mulch film reclaims very difficult, and along with the growth of duration of service and consumption, the nondegradable mulch film be trapped in soil gets more and more.White Revolution becomes white pollution, causes a series of serious problems such as soil compaction, production declining.Therefore, biodegradable polymer mould material is utilized to substitute traditional polyolefin film materials in mulch film field imperative.
The amorphous biodegradable material of carbon dioxide-epoxy propane copolymer (PPC) for utilizing carbonic acid gas to prepare, submissiveer under normal temperature, and there is the good transparency and performance of keeping humidity, its melt strength is higher, processing temperature is low, be applicable to very much making agricultural biological degradative plastic film, but the work-ing life of the carbon dioxide-epoxy propane copolymer mulch film made at present is shorter, is difficult to the service requirements meeting long-living long period farm crop.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of carbon dioxide-epoxy propane modified copolymer and preparation method thereof and carbon dioxide-base Biodegradable mulch, mulch film provided by the invention has longer work-ing life, and can be degradable rapidly after exceeding work-ing life.
The invention provides a kind of carbon dioxide-epoxy propane modified copolymer, comprise the repeating unit with formula (I) structure and the repeating unit with formula (II) structure:
In formula (II), n be 0 or 1, m be 0 or 1, R be alkylidene group.
Preferably, described R is the alkylidene group of C1 ~ C10.
Preferably, described R is for having the substituting group of formula (A), formula (B) or formula (C) structure:
---CH
2-CH
2-formula (A);---CH
2-CH
2-CH
2-CH
2-formula (B);
Preferably, the repeating unit described in formula (II) structure is specially formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5) structure:
Preferably, the mol ratio of the repeating unit in described multipolymer with formula (I) structure and the repeating unit with formula (II) structure is (0.9 ~ 0.99): (0.1 ~ 0.01).
Preferably, the number-average molecular weight of described multipolymer is 40000 ~ 150000g/mol; The molecular weight distributing index of described multipolymer is 1.8 ~ 2.8.
The invention provides a kind of preparation method of carbon dioxide-epoxy propane modified copolymer, comprise the following steps:
Propylene oxide, carbonic acid gas and formula (III) structural compounds react, obtain carbon dioxide-epoxy propane modified copolymer, described carbon dioxide-epoxy propane modified copolymer comprises the repeating unit with formula (I) structure and the repeating unit with formula (II) structure;
In formula (II) and formula (III), n be 0 or 1, m be 0 or 1, R be alkylidene group.
The invention provides a kind of carbon dioxide-base Biodegradable mulch, be made up of raw material, described raw material comprises the carbon dioxide-epoxy propane modified copolymer described in carbon dioxide-epoxy propane copolymer and technique scheme.
Preferably, the mass ratio of described carbon dioxide-epoxy propane copolymer and described carbon dioxide-epoxy propane modified copolymer is 100:(5 ~ 20).
Preferably, described raw material also comprises one or more in softening agent, uv-absorbing agent and photostabilizer.
Compared with prior art, the invention provides a kind of carbon dioxide-epoxy propane modified copolymer and preparation method thereof and carbon dioxide-base Biodegradable mulch.Biodegradable mulch provided by the invention is made up of raw material, and described raw material comprises carbon dioxide-epoxy propane copolymer and carbon dioxide-epoxy propane modified copolymer; Described carbon dioxide-epoxy propane modified copolymer comprises the repeating unit with formula (I) structure and the repeating unit with formula (II) structure.Biodegradable mulch provided by the invention with the addition of described carbon dioxide-epoxy propane modified copolymer in its preparation process, acted synergistically by described carbon dioxide-epoxy propane modified copolymer other raw materials with the described mulch film of preparation, extend the work-ing life of mulch film.Experimental result shows, Biodegradable mulch provided by the invention can reach 70 ~ 90 days work-ing life, can meet the long farm crop of growth cycle to the requirement of mulch film, and this Biodegradable mulch can be degradable rapidly after exceeding duration of service.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the epoxide group modification uv-absorbing agent hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 1 provides;
Fig. 2 is the carbon dioxide-epoxy propane modified copolymer hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 1 provides;
Fig. 3 is the epoxide group modification uv-absorbing agent hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 2 provides;
Fig. 4 is the carbon dioxide-epoxy propane modified copolymer hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 2 provides.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of carbon dioxide-epoxy propane modified copolymer, comprise the repeating unit with formula (I) structure and the repeating unit with formula (II) structure:
In formula (II), n be 0 or 1, m be 0 or 1, R be alkylidene group.
Carbon dioxide-epoxy propane modified copolymer provided by the invention comprises the repeating unit with formula (I) structure and the repeating unit with formula (II) structure.In an embodiment provided by the invention, described carbon dioxide-epoxy propane modified copolymer is made up of with the repeating unit with formula (II) structure the repeating unit with formula (I) structure.In an embodiment provided by the invention, in formula (II), described R is the alkylidene group of C1 ~ C10; In another embodiment provided by the invention, in formula (II), described R is for having the substituting group of formula (A), formula (B) or formula (C) structure:
---CH
2-CH
2-formula (A);---CH
2-CH
2-CH
2-CH
2---formula (B);
In an embodiment provided by the invention, described in there is formula (II) structure repeating unit be specially formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5) structure:
In the present invention, the repeating unit described in formula (I) structure and the random arrangement in described carbon dioxide-epoxy propane modified copolymer of the repeating unit with formula (II) structure.In an embodiment provided by the invention, the repeating unit in described multipolymer with formula (I) structure is (0.9 ~ 0.99) with the mol ratio of the repeating unit with formula (II) structure: (0.1 ~ 0.01); In another embodiment provided by the invention, the repeating unit in described multipolymer with formula (I) structure is (0.9 ~ 0.95) with the mol ratio of the repeating unit with formula (II) structure: (0.1 ~ 0.05).
In an embodiment provided by the invention, the number-average molecular weight of described multipolymer is 40000 ~ 150000g/mol, and the molecular weight distributing index of described multipolymer is 1.8 ~ 2.8; In another embodiment provided by the invention, the number-average molecular weight of described multipolymer is 42000 ~ 53000g/mol, and the molecular weight distributing index of described multipolymer is 2.1 ~ 2.8.
Carbon dioxide-epoxy propane modified copolymer provided by the invention can be used as the auxiliary agent preparing carbon dioxide-base Biodegradable mulch and uses, add described carbon dioxide-epoxy propane modified copolymer in the process preparing carbon dioxide-base Biodegradable mulch after, the work-ing life of obtained mulch film can be extended.Experimental result shows the present invention, the work-ing life being added with the Biodegradable mulch of described carbon dioxide-epoxy propane modified copolymer provided by the invention can reach 70 ~ 90 days, can meet the long farm crop of growth cycle to the requirement of mulch film, and this Biodegradable mulch can be degradable rapidly after exceeding duration of service.
The invention provides a kind of preparation method of carbon dioxide-epoxy propane modified copolymer, comprise the following steps:
Propylene oxide, carbonic acid gas and formula (III) structural compounds react, obtain carbon dioxide-epoxy propane modified copolymer, described carbon dioxide-epoxy propane modified copolymer comprises the repeating unit with formula (I) structure and the repeating unit with formula (II) structure;
In formula (II) and formula (III), n be 0 or 1, m be 0 or 1, R be alkylidene group.
In the preparation method of carbon dioxide-epoxy propane modified copolymer provided by the invention, directly propylene oxide, carbonic acid gas and formula (III) structural compounds are reacted, carbon dioxide-epoxy propane modified copolymer can be obtained.Wherein, in described formula (III) structural compounds, n be 0 or 1, m be 0 or 1, R be alkylidene group.In an embodiment provided by the invention, in formula (III), described R is the alkylidene group of C1 ~ C10; In another embodiment provided by the invention, in formula (III), described R is for having the substituting group of formula (A), formula (B) or formula (C) structure:
---CH
2-CH
2-formula (A);---CH
2-CH
2-CH
2-CH
2-formula (B);
In an embodiment provided by the invention, described formula (III) structural compounds is specially formula (III-1), formula (III-2), formula (III-3), formula (III-4) or formula (III-5) structure:
In the present invention, the source of described formula (III) structural compounds is not particularly limited, commercial commodity can be adopted, also can prepare according to method well known to those skilled in the art, can also be prepared in accordance with the following methods:
2,4-hydroxydimethylbenzene ketone and formula (IV) structural compounds react in the presence of a catalyst, obtain formula (III) structural compounds.
In the preparation method of above-mentioned formula (III) structural compounds provided by the invention, the structure of described 2,4-hydroxydimethylbenzene ketone is as follows:
In the preparation method of above-mentioned formula (III) structural compounds provided by the invention, the structure of described formula (IV) structural compounds is as follows:
In formula (IV), n be 0 or 1, m be 0 or 1, R be alkylidene group.In an embodiment provided by the invention, in formula (IV), described R is the alkylidene group of C1 ~ C10; In another embodiment provided by the invention, in formula (IV), described R is for having the substituting group of formula (A), formula (B) or formula (C) structure:
---CH
2-CH
2-formula (A);---CH
2-CH
2-CH
2-CH
2-formula (B);
In an embodiment provided by the invention, described formula (IV) structural compounds is specially formula (IV-1), formula (IV-2), formula (IV-3), formula (IV-4) or formula (IV-5) structure:
In the preparation method of above-mentioned formula (III) structural compounds provided by the invention, described catalyzer is preferably sodium hydroxide and/or ammonium nitrate; The mol ratio of described 2,4-hydroxydimethylbenzene ketone, formula (IV) structural compounds and catalyzer is preferably (4 ~ 6): (5 ~ 7): (0.2 ~ 0.5), is more preferably 5:5.5:0.38.
In the preparation method of above-mentioned formula (III) structural compounds provided by the invention, described 2,4-hydroxydimethylbenzene ketone and formula (IV) structural compounds preferably react in shielding gas atmosphere, and described shielding gas is preferably nitrogen.In the present invention, the temperature of described reaction is preferably 70 ~ 90 DEG C, is more preferably 80 ~ 85 DEG C; The time of described reaction is preferably 6 ~ 9h, is more preferably 7 ~ 8h.After reaction terminates, obtain formula (III) structural compounds.
In the preparation method of carbon dioxide-epoxy propane modified copolymer provided by the invention, described reaction is preferably carried out in the presence of a catalyst, and described catalyzer has preferably rare-earth ternary catalyst.In the present invention, described rare-earth ternary catalyst is preferably trichoroacetic acid(TCA) lanthanum-zinc ethyl-glycerol combination catalyst, trichoroacetic acid(TCA) neodymium-zinc ethyl-glycerol combination catalyst or trichoroacetic acid(TCA) yttrium-zinc ethyl-glycerol combination catalyst, is more preferably trichoroacetic acid(TCA) yttrium-zinc ethyl-glycerol combination catalyst.
In the present invention, the detailed process preparing described carbon dioxide-epoxy propane modified copolymer is in the presence of a catalyst:
First catalyzer, propylene oxide and formula (III) structural compounds are added in autoclave.Wherein, the mass ratio of described catalyzer and propylene oxide does not have special restriction, adopts well known to those skilled in the artly to prepare the catalyzer and the consumption of propylene oxide that carbon dioxide-epoxy propane copolymer adopts.Provided by the invention one adopt catalyzer be in the embodiment of trichoroacetic acid(TCA) yttrium-zinc ethyl-glycerol combination catalyst, the amount ratio of trichoroacetic acid(TCA) yttrium, zinc ethyl, glycerol and propylene oxide is preferably 1 ~ 2 (g): 3 ~ 5 (mL): 1 ~ 2 (mL): 600 ~ 1000 (mL), are more preferably 1.14 (g): 4 (mL): 1.42 (mL): 800 (mL).The mol ratio of described propylene oxide and formula (III) structural compounds is preferably 1:(0.01 ~ 0.11), be more preferably 1:(0.052 ~ 0.105).
Backward described autoclave in pass into carbonic acid gas, react.In reaction process, in described autoclave, the air pressure of carbonic acid gas is preferably 2 ~ 5MPa, is more preferably 3.5 ~ 4MPa.The temperature of described reaction is preferably 50 ~ 70 DEG C, is more preferably 60 ~ 65 DEG C; The time of described reaction is preferably 6 ~ 10h, is more preferably 8 ~ 9h.After reaction terminates, obtain carbon dioxide-epoxy propane modified copolymer, described carbon dioxide-epoxy propane modified copolymer comprises the repeating unit with formula (I) structure and the repeating unit with formula (II) structure.
The carbon dioxide-epoxy propane modified copolymer adopting method provided by the invention to obtain can be used as the auxiliary agent preparing carbon dioxide-base Biodegradable mulch and uses, add described carbon dioxide-epoxy propane modified copolymer in the process preparing carbon dioxide-base Biodegradable mulch after, the work-ing life of obtained mulch film can be extended.
The invention provides a kind of carbon dioxide-base Biodegradable mulch, be made up of raw material, described raw material comprises the carbon dioxide-epoxy propane modified copolymer described in carbon dioxide-epoxy propane copolymer and technique scheme.
Carbon dioxide-base Biodegradable mulch provided by the invention is made up of raw material, and described raw material comprises carbon dioxide-epoxy propane copolymer and described carbon dioxide-epoxy propane modified copolymer.Wherein, described carbon dioxide-epoxy propane copolymer is the chief component of mulch film provided by the invention, and other components in itself and mulch film act synergistically and obviously can extend the work-ing life of mulch film.In an embodiment provided by the invention, the melting index of described carbon dioxide-epoxy propane copolymer under 190 DEG C of probe temperatures and 2.16kg testing load is 0.5 ~ 1g/10min.
In the present invention, described carbon dioxide-epoxy propane modified copolymer by the agency of hereinbefore, does not repeat them here, and other components in described carbon dioxide-epoxy propane modified copolymer and mulch film act synergistically and obviously can extend the work-ing life of mulch film.In an embodiment provided by the invention, the mass ratio of carbon dioxide-epoxy propane copolymer described in raw material and described carbon dioxide-epoxy propane modified copolymer is 100:(5 ~ 20).
In an embodiment provided by the invention, described raw material also comprise in softening agent, uv-absorbing agent and photostabilizer one or more.In an embodiment provided by the invention, described softening agent is one or more in PEG-400, glycerine triacetate, two glycerol mono acetate bulks, tributyl citrate, Tributyl O-acetylcitrate and epoxy soybean oil.In an embodiment provided by the invention, the mass ratio of carbon dioxide-epoxy propane copolymer described in raw material and described softening agent is 100:(2 ~ 10); In another embodiment provided by the invention, the mass ratio of carbon dioxide-epoxy propane copolymer described in raw material and described softening agent is 100:(5 ~ 10).
In an embodiment provided by the invention, described uv-absorbing agent comprise in uv-absorbing agent 571, uv-absorbing agent 765, uv-absorbing agent 531 and uv-absorbing agent 234 one or more.In an embodiment provided by the invention, the mass ratio of carbon dioxide-epoxy propane copolymer described in raw material and described uv-absorbing agent is 100:(0.1 ~ 1); In another embodiment provided by the invention, the mass ratio of carbon dioxide-epoxy propane copolymer described in raw material and described uv-absorbing agent is 100:(0.2 ~ 0.5).
In an embodiment provided by the invention, described photostabilizer comprise in photostabilizer 944, photostabilizer 622, photostabilizer 770 and photostabilizer 2020 one or more.Comprise in the embodiment of photostabilizer 944, photostabilizer 622 and photostabilizer 770 at a described photostabilizer provided by the invention, the mass ratio of described photostabilizer 944, photostabilizer 622 and photostabilizer 770 is preferably (0.5 ~ 2): (0.5 ~ 2): 1, is more preferably 1:1:1.Comprise in the embodiment of photostabilizer 944 and photostabilizer 622 at a described photostabilizer provided by the invention, the mass ratio of described photostabilizer 944 and photostabilizer 622 is preferably (1 ~ 3): 1, is more preferably 2:1.In an embodiment provided by the invention, the mass ratio of carbon dioxide-epoxy propane copolymer described in raw material and described photostabilizer is 100:(0.2 ~ 2); In another embodiment provided by the invention, the mass ratio of carbon dioxide-epoxy propane copolymer described in raw material and described photostabilizer is 100:(0.4 ~ 1.5).
In an embodiment provided by the invention, the thickness of described Biodegradable mulch is 8 ~ 10 μm.
The preparation method of the present invention to described carbon dioxide-base Biodegradable mulch is not particularly limited, and is prepared according to conventional filming technology well known to those skilled in the art.In the present invention, described mulch film can be prepared in accordance with the following methods:
Raw material, successively through melt blending, granulation and blow molding, obtains carbon dioxide-base Biodegradable mulch;
In preparation method provided by the invention, first raw material carries out melt blending and granulation.Wherein, the concrete composition of described raw material by the agency of hereinbefore, does not repeat them here.In the present invention, the temperature that described raw materials melt is blended is preferably 140 ~ 180 DEG C.In the present invention, described raw material preferably carries out melt blending and granulation in dual-screw pelletizer well known to those skilled in the art.In an embodiment provided by the invention; in blended granulation process; the temperature in described dual-screw pelletizer one district is 140 DEG C; the temperature in 2nd district is 165 ± 5 DEG C, and the temperature in 3rd district is 170 ± 5 DEG C, and the temperature in 4th district is 170 ± 5 DEG C; the temperature in 5th district is 175 ± 5 DEG C; the temperature in 6th district is 175 ± 5 DEG C, and the temperature in 7th district is 165 ± 5 DEG C, and the temperature of die head is 145 DEG C.Raw material obtains plastic grain after completing melt blending and granulation.
After obtaining plastic grain, by described plastic grain blow molding.Wherein, the temperature of described blow molding is preferably 140 DEG C ~ 170 DEG C.The present invention is not particularly limited the device that described plastic grain blow molding adopts, and is preferably inflation film manufacturing machine well known to those skilled in the art.In an embodiment provided by the invention, in blow-moulding process, described inflation film manufacturing machine one district is 140 DEG C, and two district's temperature are 165 ± 5 DEG C, and three district's temperature are 165 ± 5 DEG C, and die head temperature is 170 DEG C.After plastic grain blow molding terminates, obtain carbon dioxide-base Biodegradable mulch.
Biodegradable mulch provided by the invention with the addition of described carbon dioxide-epoxy propane modified copolymer in its preparation process, acted synergistically by described carbon dioxide-epoxy propane modified copolymer other raw materials with the described mulch film of preparation, under ensureing that the mulch film made has the prerequisite of excellent biodegradable, extend the work-ing life of mulch film.Experimental result shows: the tensile strength of Biodegradable mulch thickness provided by the invention is 10 ~ 15MPa, and elongation at break is 250% ~ 360%; At senile experiment after 7 days, stretching strength retentivity is more than 50%, and elongation at break conservation rate is more than 45%, and at senile experiment after 9 days, stretching strength retentivity is greater than 45%, and elongation at break conservation rate is greater than 10%; This Biodegradable mulch can reach 70 ~ 90 days work-ing life, can meet the long farm crop of growth cycle to the requirement of mulch film, and this Biodegradable mulch can be degradable rapidly after exceeding duration of service.
For the purpose of clearer, be described in detail below by following examples.
Raw material sources used in following examples: carbon dioxide-epoxy propane copolymer used is bought by Taizhou of Zhejiang Bang Feng plastics company limited and obtained; Uv-absorbing agent used and photostabilizer are bought by BASF AG and are obtained; Softening agent used is commercially available.
Embodiment 1
1) epoxide group modification uv-absorbing agent, is prepared
By the UV-0 (2 of 1mol, 4-hydroxydimethylbenzene ketone) and 0.076mol sodium hydroxide add in 0.5L reactor, nitrogen circulation three times is led to ensure oxygen emptying with vacuum pump evacuation, add the ethylene glycol diglycidylether of 1.1mol, maintain nitrogen environment at 80 DEG C, stir, react 7 hours, obtain epoxide group modification uv-absorbing agent.
Take deuterochloroform as solvent, tetramethylsilane is interior mark, with the hydrogen nuclear magnetic resonance spectrogram of the above-mentioned obtained epoxide group modification uv-absorbing agent of BrukerAV-300 type NMR instrument record, as shown in Figure 1, Fig. 1 is the epoxide group modification uv-absorbing agent hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 1 provides to result.As seen in Figure 1, this epoxide group modification uv-absorbing agent has formula (III-3) structure:
2) carbon dioxide-epoxy propane modified copolymer, is prepared
To be trichoroacetic acid(TCA) yttrium 1.14g by the homemade ratio in laboratory, glycerine 1.42ml, the rare-earth ternary catalyst of zinc ethyl 4ml, 11.4mol propylene oxide and 1.2mol step 1) the epoxide group modification uv-absorbing agent prepared successively joins in advance through the autoclave of the deoxygenation process that dewaters, then carbonic acid gas is passed into, under the pressure, 60 DEG C of temperature of 3.5MPa, react 8 hours, obtain carbon dioxide-epoxy propane modified copolymer.
Take deuterochloroform as solvent, tetramethylsilane is interior mark, with the hydrogen nuclear magnetic resonance spectrogram of the above-mentioned obtained carbon dioxide-epoxy propane modified copolymer of BrukerAV-300 type NMR instrument record, as shown in Figure 2, Fig. 2 is the carbon dioxide-epoxy propane modified copolymer hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 1 provides to result.As seen in Figure 2, this carbon dioxide-epoxy propane modified copolymer is made up of with the repeating unit with formula (II-3) structure the repeating unit with formula (I) structure, two kinds are repeated single random arrangement, and the repeating unit in multipolymer with formula (I) structure and the repeating unit mol ratio with formula (II-3) structure are 0.9:0.1;
Detect the molecular weight and molecualr weight distribution index of described obtained carbon dioxide-epoxy propane modified copolymer, result is: number-average molecular weight is 42000g/mol, and molecular weight distributing index is 2.8.
Embodiment 2
1) epoxide group modification uv-absorbing agent, is prepared
By the UV-0 (2 of 1mol, 4-hydroxydimethylbenzene ketone) and 0.076mol sodium hydroxide add in 0.5L reactor, nitrogen circulation three times is led to ensure oxygen emptying with vacuum pump evacuation, add 1 of 1.1mol, 4-butanediol diglycidyl ether, maintains nitrogen environment and at 80 DEG C, stirs, react 7 hours, obtain epoxide group modification uv-absorbing agent.
Take deuterochloroform as solvent, tetramethylsilane is interior mark, with the hydrogen nuclear magnetic resonance spectrogram of the above-mentioned obtained epoxide group modification uv-absorbing agent of BrukerAV-300 type NMR instrument record, as shown in Figure 3, Fig. 3 is the epoxide group modification uv-absorbing agent hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 2 provides to result.As seen in Figure 3, this epoxide group modification uv-absorbing agent has formula (III-4) structure:
2) carbon dioxide-epoxy propane modified copolymer, is prepared
To be trichoroacetic acid(TCA) yttrium 1.14g by the homemade ratio in laboratory, glycerine 1.42ml, how many g rare-earth ternary catalysts of zinc ethyl 4ml, 11.4mol propylene oxide and 0.6mol step 1) the epoxide group modification uv-absorbing agent prepared successively joins in advance through the autoclave of the deoxygenation process that dewaters, then carbonic acid gas is passed into, under the pressure, 60 DEG C of temperature of 3MPa, react 8 hours, obtain carbon dioxide-epoxy propane modified copolymer.
Take deuterochloroform as solvent, tetramethylsilane is interior mark, with the hydrogen nuclear magnetic resonance spectrogram of the above-mentioned obtained carbon dioxide-epoxy propane modified copolymer of BrukerAV-300 type NMR instrument record, as shown in Figure 4, Fig. 4 is the carbon dioxide-epoxy propane modified copolymer hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 2 provides to result.As seen in Figure 4, this carbon dioxide-epoxy propane modified copolymer is made up of with the repeating unit with formula (II-4) structure the repeating unit with formula (I) structure, two kinds are repeated single random arrangement, and the repeating unit in multipolymer with formula (I) structure and the repeating unit mol ratio with formula (II-4) structure are 0.95:0.05;
Detect the molecular weight and molecualr weight distribution index of described obtained carbon dioxide-epoxy propane modified copolymer, result is: number-average molecular weight is 53000g/mol, and molecular weight distributing index is 2.1.
Embodiment 3
Prepare mulch film
Be the carbon dioxide-epoxy propane copolymer of 0.5g/10min by the melting index of 100 weight parts, the obtained carbon dioxide-epoxy propane modified copolymer of 2 weight part glycerine triacetates, 0.5 weight part uv-absorbing agent 571,0.5 weight part photostabilizer 944,0.5 weight part photostabilizer 622,0.5 weight part photostabilizer 770 and 5 parts by weight of example 1 mixes in mixing machine, then the mixture obtained is added in dual-screw pelletizer and carry out granulation, obtain plastic grain; In described granulation process, the temperature in dual-screw pelletizer one district is 140 DEG C, and the temperature in 2nd district is 165 DEG C, and the temperature in 3rd district is 170 DEG C; the temperature in 4th district is 170 DEG C, and the temperature in 5th district is 175 DEG C, and the temperature in 6th district is 175 DEG C; the temperature in 7th district is 165 DEG C, and the temperature of die head is 145 DEG C.
After obtaining plastic grain, described plastic grain is carried out blow molding on conventional preparation ground film device, and inflation film manufacturing machine temperature one district is 140 DEG C, two district's temperature are 165 DEG C, three district's temperature are 165 DEG C, and die head temperature is 170 DEG C, obtain the Biodegradable mulch that thickness is 10 microns.
Embodiment 4
Prepare mulch film
Be the carbon dioxide-epoxy propane copolymer of 0.5g/10min by the melting index of 100 weight parts, the obtained carbon dioxide-epoxy propane modified copolymer of 10 weight part PEG-400,0.5 weight part uv-absorbing agent 571,0.5 weight part photostabilizer 944,0.5 weight part photostabilizer 622,0.5 weight part photostabilizer 770 and 20 parts by weight of example 2 mixes in mixing machine, then the mixture obtained is added in dual-screw pelletizer and carry out granulation, obtain plastic grain; In described granulation process, the temperature in dual-screw pelletizer one district is 140 DEG C, and the temperature in 2nd district is 165 DEG C, and the temperature in 3rd district is 170 DEG C; the temperature in 4th district is 170 DEG C, and the temperature in 5th district is 175 DEG C, and the temperature in 6th district is 175 DEG C; the temperature in 7th district is 165 DEG C, and the temperature of die head is 145 DEG C.
After obtaining plastic grain, described plastic grain is carried out blow molding on conventional preparation ground film device, and inflation film manufacturing machine temperature one district is 140 DEG C, two district's temperature are 165 DEG C, three district's temperature are 165 DEG C, and die head temperature is 170 DEG C, obtain the Biodegradable mulch that thickness is 10 microns.
Embodiment 5
Prepare mulch film
Be the carbon dioxide-epoxy propane copolymer of 0.5g/10min by the melting index of 100 weight parts, the obtained carbon dioxide-epoxy propane modified copolymer of 10 weight part glycerine triacetates, 0.5 weight part uv-absorbing agent 234,0.5 weight part photostabilizer 944,0.5 weight part photostabilizer 622,0.5 weight part photostabilizer 770 and 20 parts by weight of example 1 mixes in mixing machine, then the mixture obtained is added in dual-screw pelletizer and carry out granulation, obtain plastic grain; In described granulation process, the temperature in dual-screw pelletizer one district is 140 DEG C, and the temperature in 2nd district is 165 DEG C, and the temperature in 3rd district is 170 DEG C; the temperature in 4th district is 170 DEG C, and the temperature in 5th district is 175 DEG C, and the temperature in 6th district is 175 DEG C; the temperature in 7th district is 165 DEG C, and the temperature of die head is 145 DEG C.
After obtaining plastic grain, described plastic grain is carried out blow molding on conventional preparation ground film device, and inflation film manufacturing machine temperature one district is 140 DEG C, two district's temperature are 165 DEG C, three district's temperature are 165 DEG C, and die head temperature is 170 DEG C, obtain the Biodegradable mulch that thickness is 10 microns.
Embodiment 6
Prepare mulch film
Be the carbon dioxide-epoxy propane copolymer of 0.5g/10min by the melting index of 100 weight parts, the obtained carbon dioxide-epoxy propane modified copolymer of 5 weight part glycerine triacetates, 0.2 weight part uv-absorbing agent 234,0.2 weight part photostabilizer 944,0.2 weight part photostabilizer 622 and 20 parts by weight of example 1 mixes in mixing machine, then the mixture obtained is added in dual-screw pelletizer and carry out granulation, obtain plastic grain; In described granulation process, the temperature in dual-screw pelletizer one district is 140 DEG C, and the temperature in 2nd district is 165 DEG C, and the temperature in 3rd district is 170 DEG C; the temperature in 4th district is 170 DEG C, and the temperature in 5th district is 175 DEG C, and the temperature in 6th district is 175 DEG C; the temperature in 7th district is 165 DEG C, and the temperature of die head is 145 DEG C.
After obtaining plastic grain, described plastic grain is carried out blow molding on conventional preparation ground film device, and inflation film manufacturing machine temperature one district is 140 DEG C, two district's temperature are 165 DEG C, three district's temperature are 165 DEG C, and die head temperature is 170 DEG C, obtain the Biodegradable mulch that thickness is 10 microns.
Comparative example
Prepare mulch film
Be the carbon dioxide-epoxy propane copolymer of 0.5g/10min, 10 weight part PEG-400,0.5 weight part uv-absorbing agent 571,0.5 weight part photostabilizer 944 by the melting index of 100 weight parts, 0.5 weight part photostabilizer 622 and 0.5 weight part photostabilizer 770 mixes in mixing machine, then the mixture obtained is added in dual-screw pelletizer and carry out granulation, obtain plastic grain; In described granulation process, the temperature in dual-screw pelletizer one district is 140 DEG C, and the temperature in 2nd district is 165 DEG C, and the temperature in 3rd district is 170 DEG C; the temperature in 4th district is 170 DEG C, and the temperature in 5th district is 175 DEG C, and the temperature in 6th district is 175 DEG C; the temperature in 7th district is 165 DEG C, and the temperature of die head is 145 DEG C.
After obtaining plastic grain, described plastic grain is carried out blow molding on conventional preparation ground film device, and inflation film manufacturing machine temperature one district is 140 DEG C, two district's temperature are 165 DEG C, three district's temperature are 165 DEG C, and die head temperature is 170 DEG C, obtain the Biodegradable mulch that thickness is 10 microns.
Embodiment 7
The present embodiment is intended to evaluate the anti ageing property of Biodegradable mulch prepared by embodiment 3 ~ 6 and comparative example, and detailed process is as follows:
By outdoor field, laying plastic and laboratory xenon lamp accelerated deterioration two kinds of methods detect the anti ageing property of mulch film on the spot.Open air laying plastic experiment is on the spot carried out in Qianan County, Jilin Province.Laboratory xenon lamp accelerated aging tests, adopts the Ci3000+ xenon lamp aging instrument of ATILAS company, and the outdoor analogy method of the 7A according to ASTMG155-05 standard carries out indoors artificial accelerated weathering test to sample.The environmental factors that the light, heat, oxygen, moisture, the rainfall that are subject in natural climate are main aging damage is simulated by artificial method.Main experimental condition is yield of radiation 0.55w/m
2wavelength is 340nm, and obtains the dependency of the accelerated deterioration of film material xenon lamp and outdoor weather aging according to standard, within one day, is equivalent to the weather aging ten days out of doors of this material by the outdoor analogy method xenon lamp aging of the 7A of ASTMG155-05 standard.
In mulch film anti ageing property testing process, as related to the test of the mechanical property of mulch film, carry out according to GB/T1040.3 stretched plastic film performance test method standard.
After Biodegradable mulch prepared by embodiment 3 ~ 6 and comparative example carries out accelerated deterioration, the test result of its ground film dynamic performance refers to table 1:
Table 1. mulch film data sheet
Contrasted by table 1 embodiment and comparative example and obtain, Biodegradable mulch ageing-resistant performance provided by the invention is excellent, can reach its work-ing life between 70 ~ 90 days, can meet the long farm crop of growth cycle to the requirement of mulch film, and this Biodegradable mulch again can be degradable rapidly after exceeding duration of service.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a carbon dioxide-epoxy propane modified copolymer, comprises the repeating unit with formula (I) structure and the repeating unit with formula (II) structure:
In formula (II), n be 0 or 1, m be 0 or 1, R be alkylidene group.
2. multipolymer according to claim 1, is characterized in that, described R is the alkylidene group of C1 ~ C10.
3. multipolymer according to claim 2, is characterized in that, described R is for having the substituting group of formula (A), formula (B) or formula (C) structure:
-CH
2-CH
2-Shi (A);-CH
2-CH
2-CH
2-CH
2-Shi (B);
4. multipolymer according to claim 3, it is characterized in that, described in there is formula (II) structure repeating unit be specially formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5) structure:
5. multipolymer according to claim 1, it is characterized in that, the repeating unit in described multipolymer with formula (I) structure is (0.9 ~ 0.99) with the mol ratio of the repeating unit with formula (II) structure: (0.1 ~ 0.01).
6. the multipolymer according to any one of Claims 1 to 5, is characterized in that, the number-average molecular weight of described multipolymer is 40000 ~ 150000g/mol; The molecular weight distributing index of described multipolymer is 1.8 ~ 2.8.
7. a preparation method for carbon dioxide-epoxy propane modified copolymer, comprises the following steps:
Propylene oxide, carbonic acid gas and formula (III) structural compounds react, obtain carbon dioxide-epoxy propane modified copolymer, described carbon dioxide-epoxy propane modified copolymer comprises the repeating unit with formula (I) structure and the repeating unit with formula (II) structure;
In formula (II) and formula (III), n be 0 or 1, m be 0 or 1, R be alkylidene group.
8. a carbon dioxide-base Biodegradable mulch, is made up of raw material, and described raw material comprises carbon dioxide-epoxy propane copolymer and the carbon dioxide-epoxy propane modified copolymer described in any one of claim 1 ~ 6.
9. mulch film according to claim 8, is characterized in that, the mass ratio of described carbon dioxide-epoxy propane copolymer and described carbon dioxide-epoxy propane modified copolymer is 100:(5 ~ 20).
10. mulch film according to claim 8, is characterized in that, described raw material also comprise in softening agent, uv-absorbing agent and photostabilizer one or more.
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