CN103232690A - Biodegradable antistatic polycaprolactone film and preparation method thereof - Google Patents
Biodegradable antistatic polycaprolactone film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a biodegradable antistatic polycaprolactone film and a preparation method thereof. The preparation method comprises: carrying out a treatment on the surface of ultrafine calcium carbonate to obtain modified ultrafine calcium carbonate; and mixing a polycaprolactone compound and the modified ultrafine calcium carbonate, carrying out melt mixing on the obtained mixture and an antistatic agent, and carrying out blow molding film preparation on the obtained master batch to obtain the biodegradable antistatic polycaprolactone film. According to the present invention, the preparation method has characteristics of simple preparation process and low cost; a rheological characteristic of the polycaprolactone film can be significantly improved with the surface-treated ultrafine calcium carbonate so as to increase moldability of the film; effects of toughening and reinforcing are provided for the polycaprolactone film, bending strength and antistatic property of the polycaprolactone film are increased, and thermal hysteresis of the polycaprolactone film is improved; and the polycaprolactone material is adopted, such that the prepared biodegradable antistatic polycaprolactone film has a characteristic of green environmental protection.
Description
Technical field
The present invention relates to a kind of biodegradable antistatic film and preparation method thereof, particularly antistatic polycaprolactone film of a kind of biodegradable and preparation method thereof.
Background technology
Polycaprolactone and multipolymer thereof are with its superior biodegradable, hypotoxicity, and good biocompatibility obtains extensive concern, it is the biodegradated polymer materal that is hopeful to obtain at present practical application most, in water and soil earth, can degrade fully, can effectively alleviate the white pollution problems that plastics such as polyethylene cause, its application can reduce carrying capacity of environment effectively, the preparation of antistatic film can substitute present nondegradable PP, PE, PET etc. are applied to the film of electronic product packing, it is Green Product, the national policy that meets energy-saving and emission-reduction has huge market potential.
Summary of the invention
The object of the present invention is to provide antistatic polycaprolactone film of a kind of biodegradable and preparation method thereof, preparation technology is simple for this method, and production cost is low, the environmental protection of the antistatic polycaprolactone film of the biodegradable that makes.
In order to achieve the above object, the antistatic polycaprolactone film of biodegradable of the present invention comprises following component: polycaprolactone compounds, modified superfine calcium carbonate and static inhibitor; Wherein, the mass ratio of polycaprolactone compounds and modified superfine calcium carbonate is 100:(10-35), the quality of static inhibitor is the 0.1-5% of polycaprolactone compounds and modified superfine calcium carbonate quality summation;
Described modified superfine calcium carbonate carries out surface treatment by silane coupling agent to calcium carbonate superfine powder and obtains, and the mass ratio of silane coupling agent and calcium carbonate superfine powder is (0.1-10): 100.
It is polycaprolactone or the polycaprolactone multipolymer of 80000-1000000 that described polycaprolactone compounds adopts molecular weight ranges.
Described polycaprolactone multipolymer comprises the mixture of one or more arbitrary proportions in caprolactone-polyalcohols multipolymer, caprolactone-amides multipolymer, caprolactone-ethers multipolymer, the caprolactone-lipin polymer.
The particle diameter of described calcium carbonate superfine powder is 20 nanometers-4000 micron.
Described silane coupling agent is γ-An Bingjisanyiyangjiguiwan (silane coupling agent KH550), γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane (silane coupling agent KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (silane coupling agent KH570), N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan (silane coupling agent KH792), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane (silane coupling agent DL602), the mixture of one or more arbitrary proportions in the vinyltrimethoxy silane (silane coupling agent DL171).
Described static inhibitor is the mixture of one or more arbitrary proportions in quaternary ammonium salt, amine salt, ethoxylation acid amides, alkyl imidazoline, alkyl imidazoline salt, phosphoric acid salt, phosphoric acid ester, sulfonate, polyvalent alcohol, polyhydric alcohol fatty acid ester, polyoxyethylene annexation, quatemay ammonium inner salt, the propylamine hydrochlorate.
Described quaternary ammonium salt is Dodecyl trimethyl ammonium chloride, the tridecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, the pentadecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, the heptadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl dimethyl hydroxyethyl ammonium perchlorate, the stearic acid trimethyl ammonium chloride, the mixture of one or more arbitrary proportions in the stearic acid dimethyl-penten ammonium chloride;
Described amine salt is the mixture of one or both arbitrary proportions in ethoxy amine hydrochloride, the ethoxylated fatty amine salt;
Described alkyl imidazoline is the mixture of one or more arbitrary proportions in undecyl imidazole quinoline, alkene acid amides ethyl type alkenyl imidazoline, quaternized heptadecyl tetrahydroglyoxaline, oleic acid base hydroxyethyl imidazole quinoline, the 1-hydroxyethyl-2-oil-based imidazoline;
Described alkyl imidazoline salt is the mixture of one or more arbitrary proportions in azo two isobutyl imidazoline salt hydrochlorates, 2-alkyl-N-hydroxyethyl imidazole quinoline third betaine, 1-carboxymethyl oxygen ethyl-1-carboxymethyl-2-alkyl imidazoline sodium salt, 1-hydroxyethyl-1-propyloic-2-alkyl imidazoline sodium salt, alkyl-beta-aminoethyl imidazoline quaternary ammonium salt, the two oil base acid amides ethyl imidazol(e) hyamine;
Described phosphoric acid salt is the mixture of one or more arbitrary proportions in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, sodium phosphate, zinc phosphate dihydrate, zinc phosphate tetrahydrate, primary zinc phosphate, monocalcium phosphate, secondary calcium phosphate, tricalcium phosphate, the alkali calcium phosphate;
Described phosphoric acid ester is the mixture of one or more arbitrary proportions in alkyl or aryl phosphoric acid ester, aliphatic alcohol polyoxyvinethene phosphate, siloxanes phosphoric acid ester, alkylol amide phosphoric acid ester, imidazolines phosphoric acid ester, the poly phosphate;
Described sulfonate is alkyl sodium sulfonate, alkyl diphenyl ether disulphonic acid, alkylbenzene sulfonate, sulfonated alkyl naphathalene, ABPS, to the mixture of one or more arbitrary proportions in the nonyl phenyl ether potassium sulfonate;
Described polyvalent alcohol is polyoxyethylene glycol;
Described polyhydric alcohol fatty acid ester is the mixture of one or more arbitrary proportions in propylene glycol octanoate, propylene glycol dicaprylate, propylene glycol dicaprate, glycerine three (thylhexoic acid) ester, trimethylolpropane tris (thylhexoic acid) ester, trimethylolpropane tris isostearate, tetramethylolmethane four (thylhexoic acid) ester, Trivent OCG, Triglyceride DDD, the butyl ethyl propane diol ethylhexoate;
Described quatemay ammonium inner salt is dodecyl dimethyl quaternary ammonium second inner salt;
Described propylamine hydrochlorate is dimethyl ethanol base stearylamide propyl ammonium nitrate.
The method for preparing the antistatic polycaprolactone film of this biodegradable may further comprise the steps:
1) calcium carbonate superfine powder is carried out surface treatment with silane coupling agent, namely get modified superfine calcium carbonate;
2) polycaprolactone compounds and modified superfine calcium carbonate are mixed, get mixture;
3) with mixture and static inhibitor 120-180 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Described step 1) modified superfine calcium carbonate adopts following method to obtain: silane coupling agent is mixed with calcium carbonate superfine powder, add ethanol, get mixed system, then mixed system was under refluxad reacted 30-240 minute, ethanol is boiled off again.
Described backflow is carried out under condition of normal pressure, 80 ℃ of reflux temperatures; Perhaps described backflow is carried out under reduced pressure, and reflux temperature is room temperature to 80 ℃.
The quality sum of the silane coupling agent that further, adds and calcium carbonate superfine powder accounts for 20% of mixed system quality.
Further, described polycaprolactone multipolymer is caprolactone-ethylene glycol segmented copolymer, caprolactone-1,4-butyleneglycol multipolymer, hexanolactam-caprolactone random copolymers, acrylamide-caprolactone graft copolymer, caprolactone-2,6-dimethyl-1, the mixture of one or more arbitrary proportions in 4-phenylate multipolymer, caprolactone-ether ether ketone multipolymer, caprolactone-lactic acid segmented copolymer, the glycollide-caprolactone copolymer.Preferably, described polycaprolactone multipolymer is caprolactone-ethylene glycol segmented copolymer, caprolactone-1, the mixture of one or more arbitrary proportions in 4-butyleneglycol multipolymer, hexanolactam-caprolactone random copolymers, acrylamide-caprolactone graft copolymer, caprolactone-lactic acid segmented copolymer, the glycollide-caprolactone copolymer.
Preferably, described caprolactone-polyalcohols multipolymer is caprolactone-ethylene glycol segmented copolymer or caprolactone-1,4-butyleneglycol multipolymer; Caprolactone-amides multipolymer is hexanolactam-caprolactone random copolymers or acrylamide-caprolactone graft copolymer; Caprolactone-ethers multipolymer is caprolactone-polyphenylene ether copolymer or caprolactone-ether ether ketone multipolymer; Caprolactone-lipin polymer is caprolactone-lactic acid segmented copolymer or glycollide-caprolactone copolymer.
Preferably, described sulfonate be sodium laurylsulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid sodium salt, alkyl naphthalene sulfonic acid ammonium salt, ABPS, to the mixture of one or more arbitrary proportions in the nonyl phenyl ether potassium sulfonate.
Preferably, described phosphoric acid ester is octadecyl phosphoric acid ester, triaryl phosphate, aliphatic alcohol polyoxyvinethene phosphate, dimethyl siloxane phosphoric acid ester, alkylol amide phosphoric acid ester, N, the mixture of one or more arbitrary proportions in N-dialkylimidazolium kind phosphate ester or the poly phosphate.
Preferably, described phosphoric acid salt comprises the mixture of one or more arbitrary proportions in sodium phosphate salt, phosphoric acid zinc salt, the calcium phosphate salt.Further preferred, described sodium phosphate salt is SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic or sodium phosphate; Phosphoric acid zinc salt is zinc phosphate dihydrate, zinc phosphate tetrahydrate or primary zinc phosphate; Calcium phosphate salt are monocalcium phosphate, secondary calcium phosphate, tricalcium phosphate or alkali calcium phosphate.
Preferably, described ethoxylation acid amides is the ethoxylated fatty acid single ethanol amide, and the polyoxyethylene annexation comprises the mixture of one or more arbitrary proportions in alkylamine, alkylamide, the polyoxyethylene.Further preferred, described polyoxyethylene annexation comprises trialkylamine, octadecylamine, N, the mixture of one or more arbitrary proportions in N-two (hydroxyethyl) laurylamide, the polyoxyethylene.
Preferably, described modified superfine calcium carbonate is that silane coupling agent is mixed with calcium carbonate superfine powder, is that solvent under refluxad reacted 30-240 minute with ethanol, boils off that ethanol obtains.
Compared with prior art, beneficial effect of the present invention is:
The present invention carries out modification with calcium carbonate superfine powder with silane coupling agent and makes modified superfine calcium carbonate, then polycaprolactone compounds, modified superfine calcium carbonate, static inhibitor are mixed, and blowing film processed namely obtains the antistatic polycaprolactone film of biodegradable.Preparation technology is simple for this method, reduced production cost, static inhibitor molecule in the antistatic polycaprolactone film of the biodegradable of making can be to external migration, form antistatic layer, therefore, the antistatic polycaprolactone film of biodegradable of the present invention can be widely used in antistatic strict electronic product packaging field; Simultaneously, the present invention has used the polycaprolactone material when the antistatic polycaprolactone film of preparation biodegradable, and therefore, the antistatic polycaprolactone film of biodegradable has excellent biodegradable performance, environmental protection.
In addition, modified superfine calcium carbonate of the present invention carries out surface treatment by silane coupling agent to calcium carbonate superfine powder and obtains, surface treated calcium carbonate superfine powder (modified superfine calcium carbonate) can reduce the tension force on calcium carbonate superfine powder surface, increases the consistency of polycaprolactone compounds calcium carbonate superfine powder; Simultaneously because the surface of the calcium carbonate superfine powder after handling lipophilicity is good, with static inhibitor consistency height, therefore can significantly improve the rheological of polycaprolactone film, improved its formability; And have the effect toughened and reinforced to the polycaprolactone film, and improve its flexural strength and antistatic property, improved it and stagnated hot.
Further; the molecular weight of polycaprolactone of the present invention or polycaprolactone multipolymer is 80000-1000000; polycaprolactone below 80000 or polycaprolactone multipolymer processing characteristics are too poor; polycaprolactone more than 1000000 or polycaprolactone multipolymer are difficult to synthetic; in the polymer research in order to improve the character of polymkeric substance; usually can be the monomer of synthetic a kind of polymkeric substance and another monomer synthetic copolymer of putting together; obtaining more high performance polymer, so polycaprolactone and multipolymer thereof have been used among the present invention.
And the particle diameter of calcium carbonate superfine powder of the present invention is 20 nanometers-4000 micron, can guarantee that surface treated calcium carbonate superfine powder (modified superfine calcium carbonate) has good dispersiveness in the antistatic polycaprolactone film of preparation biodegradable.
Embodiment
Embodiment 1:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is polycaprolactone, modified superfine calcium carbonate and the quaternary ammonium salt of 900000-1000000;
Wherein, molecular weight is that the mass ratio of calcium carbonate superfine powder is 100:10 after the polycaprolactone of 900000-1000000 and the modification; The quality of quaternary ammonium salt is that molecular weight is 2% of the polycaprolactone of 900000-1000000 and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is to be that the calcium carbonate superfine powder of 20 nanometers-1000 nanometer carries out surface treatment and obtains by γ-An Bingjisanyiyangjiguiwan to particle diameter, and γ-An Bingjisanyiyangjiguiwan and particle diameter are that the mass ratio of the calcium carbonate superfine powder of 20 nanometers-1000 nanometer is 0.1:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) be that the calcium carbonate superfine powder of 20 nanometers-1000 nanometer mixes with γ-An Bingjisanyiyangjiguiwan and particle diameter, add ethanol, get mixed system, then with mixed system 80 ℃ of following back flow reaction 30 minutes, again ethanol is boiled off with Rotary Evaporators, namely get modified superfine calcium carbonate; Wherein, the γ-An Bingjisanyiyangjiguiwan that adds and particle diameter are that the quality sum of the calcium carbonate superfine powder of 20 nanometers-1000 nanometer accounts for 20% of mixed system quality;
2) be that polycaprolactone and the modified superfine calcium carbonate of 900000-1000000 mixes with molecular weight, get mixture;
3) with mixture and quaternary ammonium salt 130 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Quaternary ammonium salt in the present embodiment is Dodecyl trimethyl ammonium chloride, the tridecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, the pentadecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, the heptadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl dimethyl hydroxyethyl ammonium perchlorate, stearic acid trimethyl ammonium chloride or stearic acid dimethyl-penten ammonium chloride.
Embodiment 2: identical with embodiment 1, polycaprolactone among the embodiment 1 is replaced with caprolactone-ethylene glycol segmented copolymer, quaternary ammonium salt replaces with quaternary ammonium mixture, and quaternary ammonium mixture is that mass ratio is the Dodecyl trimethyl ammonium chloride of 1:3 and the mixture of palmityl trimethyl ammonium chloride, mass ratio is octadecyl trimethyl ammonium chloride and the mixture of tetradecyl trimethyl ammonium chloride or the tridecyl trimethyl ammonium chloride that mass ratio is 1:2:1 of 2:1, octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl dimethyl hydroxyethyl ammonium perchlorate's mixture.
Embodiment 3: identical with embodiment 1, polycaprolactone among the embodiment 1 is replaced with caprolactone-1,4-butyleneglycol multipolymer, quaternary ammonium salt replaces with alkyl imidazoline, and alkyl imidazoline is undecyl imidazole quinoline, alkene acid amides ethyl type alkenyl imidazoline, quaternized heptadecyl tetrahydroglyoxaline, oleic acid base hydroxyethyl imidazole quinoline or 1-hydroxyethyl-2-oil-based imidazoline.
Embodiment 4: identical with embodiment 1, polycaprolactone among the embodiment 1 is replaced with hexanolactam-caprolactone random copolymers, quaternary ammonium salt among the embodiment 1 is replaced with the alkyl imidazole morpholine mixture, and the alkyl imidazole morpholine mixture is that mass ratio is the undecyl imidazole quinoline of 1:1 and the mixture of 1-hydroxyethyl-2-oil-based imidazoline, oleic acid base hydroxyethyl imidazole quinoline and the mixture of quaternized heptadecyl tetrahydroglyoxaline or the mixture of alkene acid amides ethyl type alkenyl imidazoline, undecyl imidazole quinoline and 1-hydroxyethyl-2-oil-based imidazoline that mass ratio is 2:1:1 that mass ratio is 2:5.
Embodiment 5:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is the caprolactone-2 of 8000-90000,6-dimethyl-1,4-phenylate multipolymer, modified superfine calcium carbonate and ethoxy amine hydrochloride;
Wherein, molecular weight is the caprolactone-2 of 8000-90000,6-dimethyl-1, and the mass ratio of 4-phenylate multipolymer and modified superfine calcium carbonate is 100:20; The quality of ethoxy amine hydrochloride is that molecular weight is the caprolactone-2 of 8000-90000,6-dimethyl-1,3% of 4-phenylate multipolymer and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is by γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane is that the calcium carbonate superfine powder of 200 nanometers-1000 nanometer carries out surface treatment and obtains to particle diameter, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane and particle diameter are that the mass ratio of the calcium carbonate superfine powder of 200 nanometers-1000 nanometer is 8:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) with γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane and particle diameter are that the calcium carbonate superfine powder of 200 nanometers-1000 nanometer mixes, add ethanol, get mixed system, then with mixed system under reduced pressure in 38 ℃ of following back flow reaction 160 minutes, again ethanol is boiled off with Rotary Evaporators, namely get modified superfine calcium carbonate; Wherein, the γ that adds-(2,3-epoxy, third oxygen) propyl trimethoxy silicane and particle diameter are that the calcium carbonate superfine powder quality sum of 200 nanometers-1000 nanometer accounts for 20% of mixed system quality;
2) with molecular weight be the caprolactone-2 of 8000-90000,6-dimethyl-1,4-phenylate multipolymer and modified superfine calcium carbonate mix, and get mixture;
3) with mixture and ethoxy amine hydrochloride 140 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Embodiment 6:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is polycaprolactone, modified superfine calcium carbonate and the ethoxy amine hydrochloride of 100000-150000;
Wherein, molecular weight is that the polycaprolactone of 100000-150000 and the mass ratio of modified superfine calcium carbonate are 100:20; The quality of ethoxy amine hydrochloride is that molecular weight is 3% of the polycaprolactone of 100000-150000 and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is by γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane is that the calcium carbonate superfine powder of 200 nanometers-1000 nanometer carries out surface treatment and obtains to particle diameter, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane and particle diameter are that the mass ratio of the calcium carbonate superfine powder of 200 nanometers-1000 nanometer is 8:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) with γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane and particle diameter are that the calcium carbonate superfine powder of 200 nanometers-1000 nanometer mixes, add ethanol, get mixed system, then mixed system is refluxed to send out under 38 ℃ under reduced pressure and answered 160 minutes, again ethanol is boiled off with Rotary Evaporators, namely get modified superfine calcium carbonate; Wherein, the γ that adds-(2,3-epoxy, third oxygen) propyl trimethoxy silicane and particle diameter are that the calcium carbonate superfine powder quality sum of 200 nanometers-1000 nanometer accounts for 20% of mixed system quality;
2) be that polycaprolactone and the modified superfine calcium carbonate of 100000-150000 mixes with molecular weight, get mixture;
3) with mixture and ethoxy amine hydrochloride 140 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Embodiment 7: identical with embodiment 6, polycaprolactone among the embodiment 6 is replaced with acrylamide-caprolactone graft copolymer, ethoxy amine hydrochloride replaces with the amine salt mixture, and the amine salt mixture is that mass ratio is the mixture of the ethoxy amine hydrochloride of 1:4 and dodecyl methyl polyoxyethylene ammonium chloride or ethoxy amine hydrochloride that mass ratio is 3:5 and the mixture of dodecyl methyl polyoxyethylene ammonium chloride.
Embodiment 8:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is polycaprolactone, modified superfine calcium carbonate and the ethoxylated fatty acid single ethanol amide of 200000-250000;
Wherein, molecular weight is that the polycaprolactone of 200000-250000 and the mass ratio of modified superfine calcium carbonate are 100:30; The quality of ethoxylated fatty acid single ethanol amide is that molecular weight is 4% of the polycaprolactone of 200000-250000 and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is to be that the calcium carbonate superfine powder of 2500 nanometers-10 micron carries out surface treatment and obtains by γ-(methacryloxypropyl) propyl trimethoxy silicane to particle diameter, and γ-(methacryloxypropyl) propyl trimethoxy silicane and particle diameter are that the mass ratio of the calcium carbonate superfine powder of 2500 nanometers-10 micron is 2:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) be that the calcium carbonate superfine powder of 2500 nanometers-10 micron mixes with γ-(methacryloxypropyl) propyl trimethoxy silicane and particle diameter, adding ethanol is solvent, get mixed system, then with mixed system under reduced pressure in 30 ℃ of back flow reaction 180 minutes, again ethanol is boiled off with Rotary Evaporators, namely get modified superfine calcium carbonate; Wherein, the γ that adds-(methacryloxypropyl) propyl trimethoxy silicane and particle diameter are that the quality sum of the calcium carbonate superfine powder of 2500 nanometers-10 micron accounts for 20% of mixed system quality;
2) be that polycaprolactone and the modified superfine calcium carbonate of 200000-250000 mixes with molecular weight, get mixture;
3) with mixture and ethoxylated fatty acid single ethanol amide 160 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable;
Embodiment 9: identical with embodiment 8, polycaprolactone among the embodiment 8 is replaced with caprolactone-lactic acid segmented copolymer, the ethoxylated fatty acid single ethanol amide replaces with alkyl imidazoline salt, and alkyl imidazoline salt is azo two isobutyl imidazoline salt hydrochlorates, 2-alkyl-N-hydroxyethyl imidazole quinoline third betaine, 1-carboxymethyl oxygen ethyl-1-carboxymethyl-2-alkyl imidazoline sodium salt, 1-hydroxyethyl-1-propyloic-2-alkyl imidazoline sodium salt, alkyl-beta-aminoethyl imidazoline quaternary ammonium salt or two oil base acid amides ethyl imidazol(e) hyamine.
Embodiment 10: identical with embodiment 8, ethoxylated fatty acid single ethanol amide among the embodiment 8 is replaced with the alkyl imidazoline salt mixture, and the alkyl imidazoline salt mixture is that mass ratio is the mixture of the azo two isobutyl imidazoline salt hydrochlorates of 1:2 and the mixture of 1-carboxymethyl oxygen ethyl-1-carboxymethyl-2-alkyl imidazoline sodium salt or 2-alkyl-N-hydroxyethyl imidazole quinoline third betaine that mass ratio is 2:3:1, two oil base acid amides ethyl imidazol(e) hyamine, 1-hydroxyethyl-1-propyloic-2-alkyl imidazoline sodium salt.
Embodiment 11: identical with embodiment 8, the polycaprolactone among the embodiment 8 is replaced with caprolactone-ether ether ketone multipolymer.
Embodiment 12:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is glycollide-caprolactone copolymer, modified superfine calcium carbonate and the sulfonate of 400000-500000;
Wherein, molecular weight is that glycollide-caprolactone copolymer of 400000-500000 and the mass ratio of modified superfine calcium carbonate are 100:15; The quality of sulfonate is that molecular weight is 5% of glycollide-caprolactone copolymer of 400000-500000 and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is by N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan is that the calcium carbonate superfine powder of 2000 nanometers-100 micron carries out surface treatment and obtains N-(β-aminoethyl to particle diameter)-γ-An Bingjisanjiayangjiguiwan and particle diameter are that the mass ratio of the calcium carbonate superfine powder of 2000 nanometers-100 micron is 6:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) with N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan and particle diameter are that the calcium carbonate superfine powder of 2000 nanometers-100 micron mixes, add ethanol, mixed system, then with mixed system under reduced pressure in room temperature back flow reaction 200 minutes, again ethanol is boiled off with Rotary Evaporators; Namely get modified superfine calcium carbonate; Wherein, the N-(β-aminoethyl that adds)-γ-An Bingjisanjiayangjiguiwan and particle diameter are that the quality sum of the calcium carbonate superfine powder of 2000 nanometers-100 micron accounts for 20% of mixed system quality.
2) be that glycollide-caprolactone copolymer and the modified superfine calcium carbonate of 400000-500000 mixes with molecular weight, get mixture;
3) with mixture and sulfonate 150 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Sulfonate in the present embodiment is sodium laurylsulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid sodium salt, alkyl naphthalene sulfonic acid ammonium salt, ABPS or to nonyl phenyl ether potassium sulfonate.
Embodiment 13: identical with embodiment 12, glycollide-caprolactone copolymer among the embodiment 12 is replaced with caprolactone-1,4-butyleneglycol multipolymer, sulfonate replaces with sulfonate mixtures, and sulfonate mixtures is that mass ratio is the mixture to nonyl phenyl ether potassium sulfonate and ABPS of 1:3.
Embodiment 14: identical with embodiment 12, the sulfonate among the embodiment 12 is replaced with polyoxyethylene glycol.
Embodiment 15:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is hexanolactam-caprolactone random copolymers, modified superfine calcium carbonate and the dodecyl dimethyl quaternary ammonium second inner salt of 500000-600000;
Wherein, molecular weight is that hexanolactam-caprolactone random copolymers of 500000-600000 and the mass ratio of modified superfine calcium carbonate are 100:35; The quality of dodecyl dimethyl quaternary ammonium second inner salt is that molecular weight is 0.1% of hexanolactam-caprolactone random copolymers of 500000-600000 and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is to be that the calcium carbonate superfine powder of 8000 nanometers-500 micron carries out surface treatment and obtains by N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane to particle diameter, and N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane and particle diameter are that the mass ratio of the calcium carbonate superfine powder of 8000 nanometers-500 micron is 9:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) be that 8000 nanometers-500 a micron calcium carbonate superfine powder mixes with N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane and particle diameter, add ethanol, get mixed system, then with mixed system under reduced pressure in 45 ℃ of following back flow reaction 100 minutes, again ethanol is boiled off with Rotary Evaporators, namely get modified superfine calcium carbonate; Wherein, the N-β that adds-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane and particle diameter are that the quality sum of 8000 nanometers-500 micron calcium carbonate superfine powder accounts for 20% of mixed system.
2) be that hexanolactam-caprolactone random copolymers and the modified superfine calcium carbonate of 500000-600000 mixes with molecular weight, get mixture;
3) with mixture and dodecyl dimethyl quaternary ammonium second inner salt 120 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Embodiment 16:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is polycaprolactone, modified superfine calcium carbonate and the dimethyl ethanol base stearylamide propyl ammonium nitrate of 700000-800000;
Wherein, molecular weight is that the polycaprolactone of 700000-800000 and the mass ratio of modified superfine calcium carbonate are 100:25; The quality of dimethyl ethanol base stearylamide propyl ammonium nitrate is that molecular weight is 1% of the polycaprolactone of 700000-800000 and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is to be that 400 microns-1000 microns calcium carbonate superfine powder carries out surface treatment and obtains by vinyltrimethoxy silane to particle diameter, and vinyltrimethoxy silane and particle diameter are that the mass ratio of 400 microns-1000 microns calcium carbonate superfine powder is 1:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) be that 400 microns-1000 microns calcium carbonate superfine powder mixes with vinyltrimethoxy silane and particle diameter, add ethanol, get mixed system, then with mixed system under reduced pressure in room temperature back flow reaction 240 minutes, again ethanol is boiled off with Rotary Evaporators; Namely get modified superfine calcium carbonate; Wherein, the vinyltrimethoxy silane that adds and particle diameter are that the quality sum of 400 microns-1000 microns calcium carbonate superfine powder accounts for 20% of mixed system quality;
2) be that polycaprolactone and the modified superfine calcium carbonate of 700000-800000 mixes with molecular weight, get mixture;
3) with mixture and dimethyl ethanol base stearylamide propyl ammonium nitrate in 180 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Embodiment 17: identical with embodiment 16, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 16 is replaced with polyhydric alcohol fatty acid ester, and polyhydric alcohol fatty acid ester is propylene glycol octanoate, propylene glycol dicaprylate, propylene glycol dicaprate, glycerine three (thylhexoic acid) ester, trimethylolpropane tris (thylhexoic acid) ester, trimethylolpropane tris isostearate, tetramethylolmethane four (thylhexoic acid) ester, Trivent OCG, Triglyceride DDD or butyl ethyl propane diol ethylhexoate.
Embodiment 18: identical with embodiment 16, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 16 is replaced with the polyhydric alcohol fatty acid ester mixture, and the polyhydric alcohol fatty acid ester mixture is that mass ratio is the mixture of the mixture of glycerine three (thylhexoic acid) ester of 1:4 and tetramethylolmethane four (thylhexoic acid) ester, propylene glycol octanoate, propylene glycol dicaprylate and butyl ethyl propane diol ethylhexoate that mass ratio is 1:1:1 or glycerine three (thylhexoic acid) ester that mass ratio is 2:5 and the mixture of propylene glycol dicaprylate.
Embodiment 19: identical with embodiment 16, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 16 is replaced with phosphoric acid ester, and phosphoric acid ester is octadecyl phosphoric acid ester, triaryl phosphate, aliphatic alcohol polyoxyvinethene phosphate, dimethyl siloxane phosphoric acid ester, alkylol amide phosphoric acid ester, N, N-dialkylimidazolium kind phosphate ester or poly phosphate.
Embodiment 20: identical with embodiment 16, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 16 is replaced with phosphate mixture, and phosphate mixture is that mass ratio is the mixture of the aliphatic alcohol polyoxyvinethene phosphate of 1:5 and dimethyl siloxane phosphoric acid ester or poly phosphate that mass ratio is 2:3 and the mixture of octadecyl phosphoric acid ester.
Embodiment 21: identical with embodiment 16, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 16 is replaced with phosphoric acid salt, and phosphoric acid salt is SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, sodium phosphate, zinc phosphate dihydrate, zinc phosphate tetrahydrate, primary zinc phosphate, monocalcium phosphate, secondary calcium phosphate, tricalcium phosphate or alkali calcium phosphate.
Embodiment 22: identical with embodiment 16, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 16 is replaced with phosphate mixt, and phosphate mixt is that mass ratio is the mixture of the mixture of the mixture of the SODIUM PHOSPHATE, MONOBASIC of 3:1 and zinc phosphate dihydrate, Sodium phosphate dibasic that mass ratio is 1:1 and monocalcium phosphate or sodium phosphate that mass ratio is 1:3:1, zinc phosphate tetrahydrate, alkali calcium phosphate.
Embodiment 23:
The antistatic polycaprolactone film of present embodiment biodegradable comprises following component: molecular weight is polycaprolactone, modified superfine calcium carbonate and the dimethyl ethanol base stearylamide propyl ammonium nitrate of 700000-800000;
Wherein, molecular weight is that the polycaprolactone of 700000-800000 and the mass ratio of modified superfine calcium carbonate are 100:25; The quality of dimethyl ethanol base stearylamide propyl ammonium nitrate is that molecular weight is 1% of the polycaprolactone of 700000-800000 and modified superfine calcium carbonate quality summation, and modified superfine calcium carbonate is to be that 400 microns-4000 microns calcium carbonate superfine powder carries out surface treatment and obtains by vinyltrimethoxy silane to particle diameter, and vinyltrimethoxy silane and particle diameter are that the mass ratio of 400 microns-4000 microns calcium carbonate superfine powder is 10:100.
The preparation method of the antistatic polycaprolactone film of present embodiment biodegradable is:
1) be that 400 microns-4000 microns calcium carbonate superfine powder mixes with vinyltrimethoxy silane and particle diameter, add ethanol, get mixed system, then with mixed system under reduced pressure in room temperature back flow reaction 240 minutes, again ethanol is boiled off with Rotary Evaporators; Namely get modified superfine calcium carbonate; Wherein, the vinyltrimethoxy silane that adds and particle diameter are that the quality sum of 400 microns-4000 microns calcium carbonate superfine powder accounts for 20% of mixed system quality;
2) be that polycaprolactone and the modified superfine calcium carbonate of 700000-800000 mixes with molecular weight, get mixture;
3) with mixture and dimethyl ethanol base stearylamide propyl ammonium nitrate in 180 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
Embodiment 24: identical with embodiment 23, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 23 is replaced with sulfonate that mass ratio is 1:1 and the mixture of azo two isobutyl imidazoline salt hydrochlorates, and sulfonate is sodium laurylsulfonate, dodecyl phenyl ether disulfonic acid, alkylbenzene sulfonate, sulfonated alkyl naphathalene, ABPS or to nonyl phenyl ether potassium sulfonate.
Embodiment 25: identical with embodiment 23, the dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 23 is replaced with propylene glycol octanoate that mass ratio is 3:7 and the mixture of monocalcium phosphate.
Embodiment 26: identical with embodiment 23, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 23 is replaced with the polyoxyethylene annexation, and the polyoxyethylene annexation is trialkylamine, octadecylamine, N, N-two (hydroxyethyl) laurylamide or polyoxyethylene.
Embodiment 27: identical with embodiment 23, dimethyl ethanol base stearylamide propyl ammonium nitrate among the embodiment 23 is replaced with polyoxyethylene annexation mixture, and the polyoxyethylene annexation is that mass ratio is the octadecylamine of 1:3 and the mixture of polyoxyethylene.
Embodiment 28: identical with embodiment 23, polycaprolactone among the embodiment 23 is replaced with the mixture of the caprolactone that mass ratio is 3:2-ethylene glycol segmented copolymer and caprolactone-lactic acid segmented copolymer.
Embodiment 29: identical with embodiment 23, the vinyltrimethoxy silane among the embodiment 23 is replaced with γ-An Bingjisanyiyangjiguiwan and the N-(β-aminoethyl that mass ratio is 1:1)-mixture of γ-An Bingjisanjiayangjiguiwan.
Embodiment 30: identical with embodiment 23, and be that to replace with mass ratio be that the molecular weight of 3:2 is acrylamide-caprolactone graft copolymer of 900000-1000000 and the mixture of caprolactone-lactic acid segmented copolymer that molecular weight is 800000-900000 for the polycaprolactone of 700000-800000 with molecular weight among the embodiment 23.
Claims (10)
1. the antistatic polycaprolactone film of biodegradable is characterized in that this film comprises following component: polycaprolactone compounds, modified superfine calcium carbonate and static inhibitor; Wherein, the mass ratio of polycaprolactone compounds and modified superfine calcium carbonate is 100:(10-35), the quality of static inhibitor is the 0.1-5% of polycaprolactone compounds and modified superfine calcium carbonate quality summation;
Described modified superfine calcium carbonate carries out surface treatment by silane coupling agent to calcium carbonate superfine powder and obtains, and the mass ratio of silane coupling agent and calcium carbonate superfine powder is (0.1-10): 100.
2. the antistatic polycaprolactone film of biodegradable according to claim 1 is characterized in that: it is polycaprolactone or the polycaprolactone multipolymer of 80000-1000000 that described polycaprolactone compounds adopts molecular weight ranges.
3. the antistatic polycaprolactone film of biodegradable according to claim 2, it is characterized in that: described polycaprolactone multipolymer comprises the mixture of one or more arbitrary proportions in caprolactone-polyalcohols multipolymer, caprolactone-amides multipolymer, caprolactone-ethers multipolymer, the caprolactone-lipin polymer.
4. the antistatic polycaprolactone film of biodegradable according to claim 1 is characterized in that: the particle diameter of described calcium carbonate superfine powder is 20 nanometers-4000 micron.
5. the antistatic polycaprolactone film of biodegradable according to claim 1, it is characterized in that: described silane coupling agent is γ-An Bingjisanyiyangjiguiwan, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, N-(β-aminoethyl)-mixture of one or more arbitrary proportions in the γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, vinyltrimethoxy silane.
6. the antistatic polycaprolactone film of biodegradable according to claim 1, it is characterized in that: described static inhibitor is the mixture of one or more arbitrary proportions in quaternary ammonium salt, amine salt, ethoxylation acid amides, alkyl imidazoline, alkyl imidazoline salt, phosphoric acid salt, phosphoric acid ester, sulfonate, polyvalent alcohol, polyhydric alcohol fatty acid ester, polyoxyethylene annexation, quatemay ammonium inner salt, the propylamine hydrochlorate.
7. the antistatic polycaprolactone film of biodegradable according to claim 6, it is characterized in that: described quaternary ammonium salt is Dodecyl trimethyl ammonium chloride, the tridecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, the pentadecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, the heptadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl dimethyl hydroxyethyl ammonium perchlorate, the stearic acid trimethyl ammonium chloride, the mixture of one or more arbitrary proportions in the stearic acid dimethyl-penten ammonium chloride;
Described amine salt is the mixture of one or both arbitrary proportions in ethoxy amine hydrochloride, the ethoxylated fatty amine salt;
Described alkyl imidazoline is the mixture of one or more arbitrary proportions in undecyl imidazole quinoline, alkene acid amides ethyl type alkenyl imidazoline, quaternized heptadecyl tetrahydroglyoxaline, oleic acid base hydroxyethyl imidazole quinoline, the 1-hydroxyethyl-2-oil-based imidazoline;
Described alkyl imidazoline salt is the mixture of one or more arbitrary proportions in azo two isobutyl imidazoline salt hydrochlorates, 2-alkyl-N-hydroxyethyl imidazole quinoline third betaine, 1-carboxymethyl oxygen ethyl-1-carboxymethyl-2-alkyl imidazoline sodium salt, 1-hydroxyethyl-1-propyloic-2-alkyl imidazoline sodium salt, alkyl-beta-aminoethyl imidazoline quaternary ammonium salt, the two oil base acid amides ethyl imidazol(e) hyamine;
Described phosphoric acid salt is the mixture of one or more arbitrary proportions in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, sodium phosphate, zinc phosphate dihydrate, zinc phosphate tetrahydrate, primary zinc phosphate, monocalcium phosphate, secondary calcium phosphate, tricalcium phosphate, the alkali calcium phosphate;
Described phosphoric acid ester is the mixture of one or more arbitrary proportions in alkyl or aryl phosphoric acid ester, aliphatic alcohol polyoxyvinethene phosphate, siloxanes phosphoric acid ester, alkylol amide phosphoric acid ester, imidazolines phosphoric acid ester, the poly phosphate;
Described sulfonate is alkyl sodium sulfonate, alkyl diphenyl ether disulphonic acid, alkylbenzene sulfonate, sulfonated alkyl naphathalene, ABPS, to the mixture of one or more arbitrary proportions in the nonyl phenyl ether potassium sulfonate;
Described polyvalent alcohol is polyoxyethylene glycol;
Described polyhydric alcohol fatty acid ester is the mixture of one or more arbitrary proportions in propylene glycol octanoate, propylene glycol dicaprylate, propylene glycol dicaprate, glycerine three (thylhexoic acid) ester, trimethylolpropane tris (thylhexoic acid) ester, trimethylolpropane tris isostearate, tetramethylolmethane four (thylhexoic acid) ester, Trivent OCG, Triglyceride DDD, the butyl ethyl propane diol ethylhexoate;
Described quatemay ammonium inner salt is dodecyl dimethyl quaternary ammonium second inner salt;
Described propylamine hydrochlorate is dimethyl ethanol base stearylamide propyl ammonium nitrate.
8. method for preparing the antistatic polycaprolactone film of the described biodegradable of claim 1 is characterized in that: may further comprise the steps:
1) calcium carbonate superfine powder is carried out surface treatment with silane coupling agent, namely get modified superfine calcium carbonate;
2) polycaprolactone compounds and modified superfine calcium carbonate are mixed, get mixture;
3) with mixture and static inhibitor 120-180 ℃ of following melting mixing, get masterbatch, then with masterbatch through blowing film processed, namely get the antistatic polycaprolactone film of biodegradable.
9. the method for preparing the antistatic polycaprolactone film of biodegradable according to claim 8, it is characterized in that, described step 1) modified superfine calcium carbonate adopts following method to obtain: silane coupling agent is mixed with calcium carbonate superfine powder, add ethanol, get mixed system, then mixed system was under refluxad reacted 30-240 minute, again ethanol is boiled off.
10. the method for preparing the antistatic polycaprolactone film of biodegradable according to claim 9, it is characterized in that: described backflow is carried out under condition of normal pressure, 80 ℃ of reflux temperatures; Perhaps described backflow is carried out under reduced pressure, and reflux temperature is room temperature to 80 ℃.
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