CN105367973A - High-performance environment-friendly TPE plastic wrap and preparation method thereof - Google Patents
High-performance environment-friendly TPE plastic wrap and preparation method thereof Download PDFInfo
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- CN105367973A CN105367973A CN201510795287.6A CN201510795287A CN105367973A CN 105367973 A CN105367973 A CN 105367973A CN 201510795287 A CN201510795287 A CN 201510795287A CN 105367973 A CN105367973 A CN 105367973A
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Abstract
The present invention discloses a high-performance environment-friendly TPE plastic wrap, and the starting materials include MAH-g-SEBS, MAH-g-PP, white oil, a polyquaternium-chitosan-hyperbranched polyurethane composite, an amino-terminated sulfonated polybenzimidazole prepolymer, 2,2'-bis (4-(1H-benzimidazol-2-yl) phenoxy) benzidine, a processing aid and a composite stabilizer. The present invention also discloses a preparation method of the high-performance environment-friendly TPE plastic wrap.
Description
Technical field
The invention belongs to technical field of polymer materials, more specifically, the present invention relates to a kind of high-performance environment-friendly TPE preservative film and preparation method thereof.
Background technology
At present, commercially available preservative film is mainly polyvinylidene dichloride (PVDC), polyethylene (PE) and polyvinyl chloride (PVC) three class.Wherein, polyethylene, Polrvinyl chloride preservative film use quite extensive in daily life, temporarily fresh-keeping from veterinary antibiotics to home food, and taint of odour when preventing food storage, all will use preservative film.But PE preservative film transparency is general, extension property is inadequate, is easy to break; And wretched insufficiency is there is in autohension, autohension is not strong, and plastics casing is difficult to use, package speed is slow, is unfavorable at mechanical packaging.PVC fresh-preserving film transparency is high, good-extensibility, is not easy to break, and bond properties is good, and package speed is fast, is suitable for mechanical packaging; But there is serious environmental issue, such as: the residual of vinyl chloride monomer (VCM) will cause serious harm (infringement neural system, liver and embryo) to human body, and PVC self can not biological degradation, under light/heat effect, degrade also very slow, according to burning disposal, a large amount of pungency, corrosive gases will be produced, and when burning is not thorough, also can produce the serious carcinogenic substances such as Dioxins.
Therefore, the improvement by formula and production technique is starved of, to obtain high-performance environment protection type preservative film.
Summary of the invention
In order to solve the problem, one aspect of the present invention provides a kind of high-performance environment protection type TPE preservative film, is prepared from by the raw material comprising following weight part:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 40 ~ 50 weight parts;
The white oil of 40 ~ 100 weight parts;
Polyquaternium-chitosan-super branched polyurethane the mixture of 5 ~ 20 weight parts;
The amino-terminated sulfonate polybenzimidazole prepolymer of 5 ~ 10 weight parts;
2,2'-two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of 1 ~ 5 weight part;
The processing aid of 0.1 ~ 2 weight part; With
The one package stabilizer of 0.1 ~ 2 weight part;
Wherein, described polyquaternium-chitosan-super branched polyurethane mixture by first using polyquaternium modified chitosan, then carries out modification with the modified chitosan obtained to super branched polyurethane and obtains.
In one embodiment, in described polyquaternium-chitosan-super branched polyurethane mixture, described polyquaternium is by dibenzyl bromine and Isosorbide-5-Nitrae-lupetazin 1:(0.8 ~ 0.99 in molar ratio) prepare.
In one embodiment, described amino-terminated sulfonate polybenzimidazole prepolymer is 1:(0.8 ~ 0.98 by tetramine and sulfonation diacid in molar ratio) prepare.
In one embodiment, described tetramine is selected from 3,3'-diaminobenzidine, 3,3', 4,4'-tetramino phenyl ether, 3,3', 4,4'-tetramino sulfobenzide, 3,3', 4,4'-tetramino benzophenone, 1, in 2,4,5-tetramino benzene, 1,2,5,6-tetramino naphthalene any one or multiple.
In one embodiment, described sulfonation diacid is selected from 2-sulfonic acid terephthalic acid and 4-sulfonic acid isophthalic
Any one or two kinds in dioctyl phthalate.
In one embodiment, described processing aid be selected from lipid acid, soap, fatty acid amide and
In silicone material any one or multiple.
In one embodiment, described one package stabilizer is selected from benzophenone, phosphorous acid esters, hindered phenol
In class and hindered amines material any one or multiple.
Another aspect of the present invention provides the method for described polyquaternium-chitosan-super branched polyurethane mixture,
Comprise:
A () prepares polyquaternium modified chitosan:
In 100ml three-necked bottle, add chitosan 0.1mol and described polyquaternium 0.01 ~ 0.2mol, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.01 ~ 0.3mol and with after water dissolution, add said mixture, reacting after 10 ~ 24 hours at 30 ~ 60 DEG C, neutralize with Hydrogen bromide and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan.
B () prepares hyperbranched:
Vulcabond and trivalent alcohol are dissolved in polar solvent respectively, obtain diisocyanate solution respectively
With trivalent alcohol solution, controlling its mass concentration is 5 ~ 30%; Wherein, vulcabond is isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate or 2,4 tolylene diisocyanates; Described trivalent alcohol is glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol;
30 ~ 100 DEG C, under protective atmosphere, limit is stirred, and diisocyanate solution is added to trivalent alcohol molten
In liquid, wherein the mol ratio of the isocyanato of vulcabond and the hydroxyl of trivalent alcohol is 9:8 ~ 3:1; After vulcabond has added, reaction system insulation reaction 10 ~ 30h; Then in reaction system, add protective material, at 30 ~ 100 DEG C, continue reaction 5 ~ 10h;
After end, after underpressure distillation goes out solvent, dissolved by gained material through tetrahydrofuran (THF), sedimentation and after filtering in methyl alcohol, by its vacuum-drying 10 ~ 24h at 50 ~ 140 DEG C, obtains the super branched polyurethane containing isocyanato of purifying;
C () prepares polyquaternium-chitosan-super branched polyurethane mixture:
In 100ml three-necked bottle, add the polyquaternium modified chitosan 0.1 gram of above-mentioned synthesis, super branched polyurethane 0.2 ~ 2 gram and DMF 50ml, after stirred at ambient temperature is even; React after 10 ~ 24 hours at 30 ~ 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture.
Another aspect again of the present invention provides a kind of method preparing high-performance environment protection type TPE preservative film, comprises the steps:
Get described raw material, use twin screw extruder granulation; Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film;
Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 ~ 200 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, head temperature 185 ~ 200 DEG C;
Thin film extruding machine host machine part temperature is for from charging opening, and be followed successively by 150 ~ 160 DEG C, 165 ~ 175 DEG C, 170 ~ 180 DEG C, 175 ~ 185 DEG C, 180 ~ 190 DEG C, head section temperature is 175 ~ 185 DEG C.
In one embodiment, the described method preparing high-performance environment protection type TPE preservative film, also comprises:
The antistaling film obtained is immersed in polyphosphoric acid, keeps after 3 ~ 8 hours at 120 ~ 180 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain preservative film crosslinked further.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised more easily can understand present disclosure.Can mention a large amount of term in following specification sheets and claims, these terms are defined as following implication.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context.
" optional " or " optionally " refers to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
One aspect of the present invention provides a kind of high-performance environment protection type TPE preservative film, is prepared from by the raw material comprising following weight part:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 40 ~ 50 weight parts;
The white oil of 40 ~ 100 weight parts;
Polyquaternium-chitosan-super branched polyurethane the mixture of 5 ~ 20 weight parts;
The amino-terminated sulfonate polybenzimidazole prepolymer of 5 ~ 10 weight parts;
2,2'-two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of 1 ~ 5 weight part;
The processing aid of 0.1 ~ 2 weight part; With
The one package stabilizer of 0.1 ~ 2 weight part;
Wherein, described polyquaternium-chitosan-super branched polyurethane mixture by first using polyquaternium modified chitosan, then carries out modification with the modified chitosan obtained to super branched polyurethane and obtains.
The term " SEBS " used in the application refers to polystyrene to be end segment, and the ethylene-butene copolymer obtained with polyhutadiene hydrogenation is the linear three block copolymer of middle spring block.
Maleic anhydride modified SEBS(MAH-g-SEBS in the application) be not particularly limited, can be commercially available or experiment synthesis, such as, can adopt solution graft copolymerization and fusion-grafting two kinds of methods synthesis, wherein, when solution grafting carries out SEBS grafting MAH, the graft reaction time is long, and grafting efficiency is low, need to consume poisonous, flammable solvent in a large number, production cost is high, large to human injury, contaminate environment, take up an area large, be difficult to realize continuous operation.Therefore, preferably melt grafting is adopted.
In one embodiment, in described MAH-g-SEBS, the percentage of grafting of MAH is 1% ~ 3%; Preferably, in described MAH-g-SEBS, the percentage of grafting of MAH is 2%.
Maleic anhydride modified PP(MAH-g-PP as using in the present invention) be not particularly limited, can be commercially available or experiment synthesis, wherein, the percentage of grafting of MAH can be 1% ~ 3%; Preferably, the percentage of grafting of MAH is 2%.
The term " polyquaternium-chitosan-super branched polyurethane mixture " used in the application refers to and first uses polyquaternium modified chitosan, then carries out modification with the modified chitosan obtained to super branched polyurethane and obtain.
In one embodiment, in described polyquaternium-chitosan-super branched polyurethane mixture, described polyquaternium is by dibenzyl bromine and Isosorbide-5-Nitrae-lupetazin 1:(0.8 ~ 0.99 in molar ratio) prepare; Preferably, described polyquaternium by dibenzyl bromine and Isosorbide-5-Nitrae-lupetazin in molar ratio 1:0.9 prepare.
The concrete preparation method of described polyquaternium can be:
In 100ml three-necked bottle, add dibenzyl bromine 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.08 ~ 0.099mol and solvent DMF 50ml, react after 10 ~ 24 hours at 40 ~ 60 DEG C, underpressure distillation is removed solvent and is obtained polyquaternium.
Super branched polyurethane for the application is standby by employing A2+B3 legal system, and obtains isocyanate-terminated polymkeric substance, and concrete grammar is:
1) vulcabond and trivalent alcohol are dissolved in respectively in polar solvent, obtain diisocyanate solution and trivalent alcohol solution respectively, controlling its mass concentration is 5 ~ 30%; Wherein, vulcabond is isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate or 2,4 tolylene diisocyanates; Described trivalent alcohol is glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol;
2) 30 ~ 100 DEG C, under protective atmosphere, limit is stirred, and be added to by diisocyanate solution in trivalent alcohol solution, wherein the mol ratio of the isocyanato of vulcabond and the hydroxyl of trivalent alcohol is 9:8 ~ 3:1; After vulcabond has added, reaction system insulation reaction 10 ~ 30h; Then in reaction system, add protective material, at 30 ~ 100 DEG C, continue reaction 5 ~ 10h;
3) after reaction terminates, after underpressure distillation goes out solvent, dissolved by gained material through tetrahydrofuran (THF), sedimentation and after filtering in methyl alcohol, by its vacuum-drying 10 ~ 24h at 50 ~ 140 DEG C, obtains the super branched polyurethane containing isocyanato of purifying;
Preferably, the mol ratio of the isocyanato of described vulcabond and the hydroxyl of trivalent alcohol is 2:1.
In one embodiment, the solvent that described diisocyanate solution, trivalent alcohol solution adopt is dimethyl sulfoxide (DMSO), N, the mixing of one or more in N-N,N-DIMETHYLACETAMIDE, DMF, N, N-dimethyl pyrrolidone, tetrahydrofuran (THF) or toluene.
In one embodiment, described protective material is phenol, hexanolactam, ethylene glycol ethyl ether or methyl ethyl ketoxime; Protectant add-on is 1 ~ 60% of vulcabond mole number.
Polyquaternium-chitosan-super branched polyurethane mixture for the application can obtain especially by following methods:
A () prepares polyquaternium modified chitosan:
In 100ml three-necked bottle, add the polyquaternium 0.01 ~ 0.2mol of chitosan 0.1mol and above-mentioned synthesis, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.01 ~ 0.3mol and with after water dissolution, add said mixture, reacting after 10 ~ 24 hours at 30 ~ 60 DEG C, neutralize with Hydrogen bromide and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan.
B () prepares polyquaternium-chitosan-super branched polyurethane mixture:
In 100ml three-necked bottle, add the polyquaternium modified chitosan 0.1 gram of above-mentioned synthesis, super branched polyurethane 0.2 ~ 2 gram and DMF 50ml, after stirred at ambient temperature is even; React after 10 ~ 24 hours at 30 ~ 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture;
Preferably, the weight ratio of described polyquaternium modified chitosan and super branched polyurethane is 1:5.
Adding of polyquaternium-chitosan-super branched polyurethane mixture can be concentrated by a large amount of of polyquaternium on the one hand, play good antibacterial effect, on the other hand, also can under the prerequisite not affecting processing characteristics, play certain crosslinked action, improve intensity and the wear resisting property of shoe-pad, in addition, special hyperbranched globosity can also ensure the consistency good with SEBS and provide better elasticity, because herein is provided Advantageous Effects of the present invention.
It is to be noted that the type of quaternary ammonium salt and stability have much relations, adopt bromotoluene to replace conventional aliphatic chain bromine in the application, the stability of quaternary ammonium salt can be improved significantly, thus improve the stability of anti-microbial property.
Term " amino-terminated sulfonate polybenzimidazole prepolymer " in the application refers to the amino-terminated prepolymer be obtained by reacting by sulfonation diacid and excessive tetramine, mol ratio for sulfonation diacid and tetramine is not particularly limited, as long as tetramine is excessive, but preferably, described amino-terminated sulfonate polybenzimidazole prepolymer is by comprising mol ratio for (0.8 ~ 0.98): the sulfonation diacid of 1 and the raw material of tetramine prepare; More preferably, described amino-terminated sulfonate polybenzimidazole prepolymer is that the sulfonation diacid of 0.95:1 and the raw material of tetramine prepare by comprising mol ratio.
Described amino-terminated sulfonate polybenzimidazole prepolymer can be prepared especially by following methods:
The sulfonation diacid of formula ratio and excessive tetramine are dissolved in polyphosphoric acid; logical nitrogen protection 0.5 as a child; after being warming up to 180 DEG C of reaction 24h; reaction solution is poured in frozen water; then neutralizing this aqueous solution to PH with sodium hydroxide is 5 ~ 6; then suction filtration the precipitation that obtains with deionized water repetitive scrubbing, is finally deposited in 80 DEG C of dry 10h in vacuum drying oven, obtains final product by this.
In one embodiment, described sulfonation diacid is selected from any one or two kinds in 2-sulfonic acid terephthalic acid and 5-sulfonic acid m-phthalic acid; Preferably, described sulfonation diacid is 2-sulfonic acid terephthalic acid.
In one embodiment, described tetramine is selected from 3,3'-diaminobenzidine, 3,3', 4,4'-tetramino phenyl ether, 3,3', 4,4'-bis-amido sulfobenzide, 3,3', 4,4'-bis-aminobenzophenones, 3,3', 4,4'-bis-amido hexichol first, 3,3', 4,4'-bis-amido diphenyl sulfide, 1,2,4, in 5-tetra-amido benzene or 1,2,5,6-tetra-amido naphthalene any one or multiple; Preferably, described tetramine is selected from 3,3'-diaminobenzidine, 3,3', 4,4'-bis-amido sulfobenzide and 3,3', in 4,4'-bis-aminobenzophenone any one or multiple; More preferably, described tetramine is 3,3'-diaminobenzidine.
Adding of amino-terminated sulfonate polybenzimidazole prepolymer can use as antioxidant, in addition the stability of system can also be significantly improved, meanwhile, because the activity of tetramine is very high, be easy to and anhydride reaction, thus improve the degree of crosslinking of system, and provide Advantageous Effects of the present invention.
For 2,2'-two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of the application, its chemical structure is as follows:
;
Its preparation method is:
First preparing 50g Vanadium Pentoxide in FLAKES mass concentration is that the poly phosphoric acid solution of 85wt% is as solvent, under nitrogen protection, in the 100mL three-necked bottle of abundant drying, add 4.69g(0.01mol) 2, two (4-carboxyphenoxy) p-diaminodiphenyl of 2'-, 2.27g(0.021mol) O-Phenylene Diamine, after solid fully dissolves, react 24 hours at 180 DEG C, reaction terminates rear system and is cooled to about 80 DEG C, resultant is poured in deionized water, extremely neutral with sodium hydrogen carbonate solution washing afterwards, use deionized water wash again, be finally the N of 1:1 by volume ratio, the mixing solutions of dinethylformamide and water carries out recrystallization, the recrystallized product obtained was 60 DEG C of vacuum-dryings 12 hours, obtain 2, two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of 2'-.
2, two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of 2'-both can improve cross-linking density, again can by the introducing of imidazoles, produce ionomer and improve the weathering resistance of strand material, because herein is provided Advantageous Effects of the present invention.
In order to improve processing characteristics, in the application, the raw materials of the high antibacterial TPE Shock absorption shoe-pad of high strength also can comprise the processing aid of 0.1 ~ 2 weight part and the one package stabilizer of 0.1 ~ 2 weight part;
Wherein, processing aid can be at least one in lipid acid, soap, fatty acid amide, silicone material;
One package stabilizer can be the mixture of benzophenone, phosphorous acid esters, Hinered phenols, hindered amines light and/or these compounds, as: UV-531, Irganox1010, Irganox168, Irganox1076 of Ciba Specialty Chemicals; Antioxygen, anti copper agent MD-1024 etc. that Li Anlong (Tianjin) Industrial Co., Ltd. produces.
Another aspect of the present invention provides a kind of method preparing high-performance environment protection type TPE preservative film, comprises the steps:
Get described raw material, use twin screw extruder granulation; Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film;
Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 ~ 200 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, head temperature 185 ~ 200 DEG C;
Thin film extruding machine host machine part temperature is for from charging opening, and be followed successively by 150 ~ 160 DEG C, 165 ~ 175 DEG C, 170 ~ 180 DEG C, 175 ~ 185 DEG C, 180 ~ 190 DEG C, head section temperature is 175 ~ 185 DEG C.
In one embodiment, the described method preparing high-performance environment protection type TPE preservative film, also comprises:
The antistaling film obtained is immersed in polyphosphoric acid, keeps after 3 ~ 8 hours at 120 ~ 180 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain preservative film crosslinked further.
Due in system containing carboxyl and sulfonic group, therefore by the pyroprocessing of vacuum and polyphosphoric acid, can with the phenyl ring generation friedel-crafts acylation of richness electricity, thus the degree of crosslinking of raising system further, and Advantageous Effects of the present invention is provided.
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available, and following material number used is weight part.
Raw material:
A1:MAH-g-SEBS(MAH percentage of grafting 1%)
A2:MAH-g-SEBS(MAH percentage of grafting 2%)
A3:MAH-g-SEBS(MAH percentage of grafting 3%)
B1:MAH-g-PP(MAH percentage of grafting 1%)
B2:MAH-g-PP(MAH percentage of grafting 2%)
B3:MAH-g-PP(MAH percentage of grafting 3%)
C1: white oil
D1: polyquaternium-chitosan-super branched polyurethane mixture, its preparation method is:
(1) polyquaternium is prepared
In 100ml three-necked bottle, add dibenzyl bromine 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.08mol and solvent DMF 50ml, react after 15 hours at 50 DEG C, underpressure distillation is removed solvent and is obtained polyquaternium;
(2) polyquaternium modified chitosan is prepared
In 100ml three-necked bottle, add the polyquaternium 0.01mol of chitosan 0.1mol and above-mentioned synthesis, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.1mol and with after water dissolution, add said mixture, reacting after 12 hours at 50 DEG C, neutralize with acetic acid and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan;
(3) super branched polyurethane is prepared
The isophorone diisocyanate of 0.027 mole is dissolved in the toluene of 20mL, obtain diisocyanate solution, then 0.016 mole of glycerol is dissolved in 20mL dimethyl sulphoxide solution, obtain trivalent alcohol solution, then described trivalent alcohol solution is joined in the there-necked flask of band magnetic agitation and reflux, 40 DEG C, under nitrogen protection, slowly add the toluene solution of described isophorone diisocyanate under stirring wherein;
After dripping, system continues to react 10h at 40 DEG C, in reaction medium, then add the phenol of 0.002 mole, and heating, reacts 5h at 100 DEG C;
After reaction terminates, underpressure distillation goes out solvent.Products therefrom methyl alcohol-tetrahydrofuran (THF) (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, 60 DEG C of vacuum-drying 24h, obtain super branched polyurethane;
(4) polyquaternium-chitosan-super branched polyurethane mixture is prepared
In 100ml three-necked bottle, add the polyquaternium-chitosan-super branched polyurethane mixture 0.1 gram of above-mentioned synthesis, super branched polyurethane 0.2 gram and DMF 50ml, after stirred at ambient temperature is even; React after 10 hours at 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture
D2: polyquaternium-chitosan-super branched polyurethane mixture, its preparation method is:
(1) polyquaternium is prepared
In 100ml three-necked bottle, add dibenzyl bromine 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.099mol and solvent DMF 50ml, react after 15 hours at 50 DEG C, underpressure distillation is removed solvent and is obtained polyquaternium;
(2) polyquaternium modified chitosan is prepared
In 100ml three-necked bottle, add the polyquaternium 0.2mol of chitosan 0.1mol and above-mentioned synthesis, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.1mol and with after water dissolution, add said mixture, reacting after 12 hours at 50 DEG C, neutralize with acetic acid and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan;
(3) super branched polyurethane is prepared
4 ' the 4-diphenylmethanediisocyanate of 0.09 mole is dissolved in the toluene of 20mL, obtain diisocyanate solution, then 0.02 mole of trimethylol propane is dissolved in 20mL dimethyl sulphoxide solution, obtain trivalent alcohol solution, then described trivalent alcohol solution is joined in the there-necked flask of band magnetic agitation and reflux, 40 DEG C, under nitrogen protection, slowly add the toluene solution of 4 ' described 4-diphenylmethanediisocyanate under stirring wherein;
After dripping, system continues to react 10h at 40 DEG C, in reaction medium, then add the hexanolactam of 0.002 mole, and heating, reacts 5h at 100 DEG C;
After reaction terminates, underpressure distillation goes out solvent.Products therefrom methyl alcohol-tetrahydrofuran (THF) (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, 60 DEG C of vacuum-drying 24h, obtain super branched polyurethane;
(4) polyquaternium-chitosan-super branched polyurethane mixture is prepared
In 100ml three-necked bottle, add the polyquaternium-chitosan-super branched polyurethane mixture 0.1 gram of above-mentioned synthesis, super branched polyurethane 2 grams and DMF 50ml, after stirred at ambient temperature is even; React after 10 hours at 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture
D3: polyquaternium-chitosan-super branched polyurethane mixture, its preparation method is:
(1) polyquaternium is prepared
In 100ml three-necked bottle, add dibenzyl bromine 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.095mol and solvent DMF 50ml, react after 15 hours at 50 DEG C, underpressure distillation is removed solvent and is obtained polyquaternium;
(2) polyquaternium modified chitosan is prepared
In 100ml three-necked bottle, add the polyquaternium 0.1mol of chitosan 0.1mol and above-mentioned synthesis, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.1mol and with after water dissolution, add said mixture, reacting after 12 hours at 50 DEG C, neutralize with acetic acid and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan;
(3) super branched polyurethane is prepared
4 ' the 4-diphenylmethanediisocyanate of 0.09 mole is dissolved in the toluene of 20mL, obtain diisocyanate solution, then 0.02 mole of trimethylol propane is dissolved in 20mL dimethyl sulphoxide solution, obtain trivalent alcohol solution, then described trivalent alcohol solution is joined in the there-necked flask of band magnetic agitation and reflux, 40 DEG C, under nitrogen protection, slowly add the toluene solution of 4 ' described 4-diphenylmethanediisocyanate under stirring wherein;
After dripping, system continues to react 10h at 40 DEG C, in reaction medium, then add the hexanolactam of 0.002 mole, and heating, reacts 5h at 100 DEG C;
After reaction terminates, underpressure distillation goes out solvent.Products therefrom methyl alcohol-tetrahydrofuran (THF) (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, 60 DEG C of vacuum-drying 24h, obtain super branched polyurethane;
(4) polyquaternium-chitosan-super branched polyurethane mixture is prepared
In 100ml three-necked bottle, add the polyquaternium-chitosan-super branched polyurethane mixture 0.1 gram of above-mentioned synthesis, super branched polyurethane 1 gram and DMF 50ml, after stirred at ambient temperature is even; React after 10 hours at 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture
D4: polyquaternium-chitosan-super branched polyurethane mixture, its preparation method is:
(1) polyquaternium is prepared
In 100ml three-necked bottle, add dibenzyl bromine 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.095mol and solvent DMF 50ml, react after 15 hours at 50 DEG C, underpressure distillation is removed solvent and is obtained polyquaternium;
(2) polyquaternium modified chitosan is prepared
In 100ml three-necked bottle, add the polyquaternium 0.1mol of chitosan 0.1mol and above-mentioned synthesis, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.1mol and with after water dissolution, add said mixture, reacting after 12 hours at 50 DEG C, neutralize with acetic acid and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan;
(3) super branched polyurethane is prepared
4 ' the 4-diphenylmethanediisocyanate of 0.09 mole is dissolved in the toluene of 20mL, obtain diisocyanate solution, then 0.02 mole of trimethylol propane is dissolved in 20mL dimethyl sulphoxide solution, obtain trivalent alcohol solution, then described trivalent alcohol solution is joined in the there-necked flask of band magnetic agitation and reflux, 40 DEG C, under nitrogen protection, slowly add the toluene solution of 4 ' described 4-diphenylmethanediisocyanate under stirring wherein;
After dripping, system continues to react 10h at 40 DEG C, in reaction medium, then add the hexanolactam of 0.002 mole, and heating, reacts 5h at 100 DEG C;
After reaction terminates, underpressure distillation goes out solvent.Products therefrom methyl alcohol-tetrahydrofuran (THF) (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, 60 DEG C of vacuum-drying 24h, obtain super branched polyurethane;
(4) polyquaternium-chitosan-super branched polyurethane mixture is prepared
In 100ml three-necked bottle, add the polyquaternium-chitosan-super branched polyurethane mixture 0.1 gram of above-mentioned synthesis, super branched polyurethane 1 gram and DMF 50ml, after stirred at ambient temperature is even; React after 10 hours at 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture
D5: polyquaternium-chitosan-super branched polyurethane mixture, its preparation method is:
(1) polyquaternium is prepared
In 100ml three-necked bottle, add dibenzyl bromine 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.09mol and solvent DMF 50ml, react after 15 hours at 50 DEG C, underpressure distillation is removed solvent and is obtained polyquaternium;
(2) polyquaternium modified chitosan is prepared
In 100ml three-necked bottle, add the polyquaternium 0.1mol of chitosan 0.1mol and above-mentioned synthesis, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.1mol and with after water dissolution, add said mixture, reacting after 12 hours at 50 DEG C, neutralize with acetic acid and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan;
(3) super branched polyurethane is prepared
4 ' the 4-diphenylmethanediisocyanate of 0.09 mole is dissolved in the toluene of 20mL, obtain diisocyanate solution, then 0.02 mole of trimethylol propane is dissolved in 20mL dimethyl sulphoxide solution, obtain trivalent alcohol solution, then described trivalent alcohol solution is joined in the there-necked flask of band magnetic agitation and reflux, 40 DEG C, under nitrogen protection, slowly add the toluene solution of 4 ' described 4-diphenylmethanediisocyanate under stirring wherein;
After dripping, system continues to react 10h at 40 DEG C, in reaction medium, then add the methyl ethyl ketoxime of 0.002 mole, and heating, reacts 5h at 100 DEG C;
After reaction terminates, underpressure distillation goes out solvent.Products therefrom methyl alcohol-tetrahydrofuran (THF) (volume ratio (1/10)) dissolving, sedimentation 3 times, filter, 60 DEG C of vacuum-drying 24h, obtain super branched polyurethane;
(4) polyquaternium-chitosan-super branched polyurethane mixture is prepared
In 100ml three-necked bottle, add the polyquaternium-chitosan-super branched polyurethane mixture 0.1 gram of above-mentioned synthesis, super branched polyurethane 0.5 gram and DMF 50ml, after stirred at ambient temperature is even; React after 10 hours at 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture.
D6: polyquaternium-chitosan-super branched polyurethane mixture, its preparation method is similar to C5, and difference is only to replace dibenzyl bromine with 1,12-dibromo-dodecane
E1: amino-terminated sulfonate polybenzimidazole prepolymer (2-sulfonic acid terephthalic acid and 3,3', 4,4'-tetramino phenyl ether in molar ratio 0.8:1 prepares)
E2: amino-terminated sulfonate polybenzimidazole prepolymer (2-sulfonic acid terephthalic acid and 3,3', 4,4'-bis-amido diphenyl sulfide in molar ratio 0.98:1 prepares)
E3: amino-terminated sulfonate polybenzimidazole prepolymer (2-sulfonic acid terephthalic acid and 3,3', 4,4'-bis-amido diphenyl sulfide in molar ratio 0.95:1 prepares)
E4: amino-terminated sulfonate polybenzimidazole prepolymer (5-sulfonic acid m-phthalic acid and 3,3', 4,4'-bis-amido sulfobenzide in molar ratio 0.95:1 prepares)
E5: amino-terminated sulfonate polybenzimidazole prepolymer (2-sulfonic acid terephthalic acid and 3,3'-diaminobenzidine in molar ratio 0.95:1 prepare)
Two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of F1:2,2'-
G1: hard fatty acids
G2: calcium stearate
H1：UV-9
H2: three (2,4-di-tert-butyl-phenyl) phosphorous acid ester
Embodiment 1
By the H1 of the F1 of the E1 of the D1 of the C1 of the B1 of the A1 of 100 weight parts, 40 weight parts, 40 weight parts, 5 weight parts, 5 weight parts, 1 weight part, the G1 of 0.1 weight part and 0.1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 2
By the H1 of the F1 of the E1 of the D1 of the C1 of the B2 of the A2 of 100 weight parts, 40 weight parts, 40 weight parts, 5 weight parts, 5 weight parts, 1 weight part, the G1 of 0.1 weight part and 0.1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 3
By the H1 of the F1 of the E1 of the D1 of the C1 of the B3 of the A3 of 100 weight parts, 40 weight parts, 40 weight parts, 5 weight parts, 5 weight parts, 1 weight part, the G1 of 0.1 weight part and 0.1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 4
By the H1 of the F1 of the E1 of the D1 of the C1 of the B2 of the A2 of 100 weight parts, 50 weight parts, 50 weight parts, 20 weight parts, 10 weight parts, 5 weight parts, the G1 of 2 weight parts and 2 weight parts, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 5
By the H1 of the F1 of the E2 of the D2 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, 8 weight parts, 3 weight parts, the G1 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 6
By the H2 of the F1 of the E3 of the D3 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, 8 weight parts, 3 weight parts, the G2 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 7
By the H2 of the F1 of the E4 of the D4 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, 8 weight parts, 3 weight parts, the G1 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 8
By the H2 of the F1 of the E5 of the D5 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, 8 weight parts, 3 weight parts, the G2 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 9
By the H2 of the F1 of the E5 of the D6 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, 8 weight parts, 3 weight parts, the G2 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Embodiment 10
By the H1 of the F1 of the E5 of the D5 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, 8 weight parts, 3 weight parts, the G1 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Comparative example 1
By the H1 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, the G1 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Comparative example 2
By the H1 of the D1 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, the G1 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Comparative example 3
By the H1 of the E5 of the D1 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, 8 weight parts, the G1 of 1 weight part and 1 weight part, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Comparative example 4
By the F1 of the D1 of the C1 of the B2 of the A2 of 100 weight parts, 45 weight parts, 45 weight parts, 10 weight parts, the E5 of 8 weight parts and 3 weight parts, by weight after mixing, through double-screw extruding pelletizing; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, 205 DEG C, head temperature 195 DEG C;
Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film; Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 205 DEG C, 205 DEG C, head temperature 200 DEG C;
Finally, the antistaling film obtained is immersed in polyphosphoric acid, keeps after 5 hours at 160 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain antistaling film crosslinked further.
Comparative example 5
Similar to embodiment 7 method, difference is not adopt polyphosphoric acid to carry out crosslinking reaction further.
testing method
Above-described embodiment 1 ~ 10 and comparative example 1 ~ 5 are prepared into strip, and test, testing method is as follows:
Tensile property: tensile strength and elongation at break measure according to JISK6251.
Anti-microbial property: measure according to Japanese Industrial Standards JISZ2801.
Antibacterial stability: made sample is immersed in the water of 80 DEG C, after one week, test the loss amount of its anti-microbial activity value, its method of calculation are: intestinal bacteria anti-microbial activity value before activity value loss amount=(before test the rear intestinal bacteria anti-microbial activity value of intestinal bacteria anti-microbial activity value-test)/test.
Test result is in table 1.
Table 1
Above data can be found out, with do not use polyquaternium-chitosan-super branched polyurethane mixture, amino-terminated sulfonate polybenzimidazole prepolymer and 2, the product of two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of 2'-is compared, high-performance environment protection type TPE preservative film prepared by the present invention is while possessing high strength, also there is good anti-microbial property, because herein is provided Advantageous Effects of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. high-performance environment protection type TPE preservative film, is prepared from by the raw material comprising following weight part:
The MAH-g-SEBS of 100 weight parts;
The MAH-g-PP of 40 ~ 50 weight parts;
The white oil of 40 ~ 100 weight parts;
Polyquaternium-chitosan-super branched polyurethane the mixture of 5 ~ 20 weight parts;
The amino-terminated sulfonate polybenzimidazole prepolymer of 5 ~ 10 weight parts;
2,2'-two (4-(1H-benzimidazolyl-2 radicals-Ji) phenoxy group) p-diaminodiphenyl of 1 ~ 5 weight part;
The processing aid of 0.1 ~ 2 weight part; With
The one package stabilizer of 0.1 ~ 2 weight part;
Wherein, described polyquaternium-chitosan-super branched polyurethane mixture by first using polyquaternium modified chitosan, then carries out modification with the modified chitosan obtained to super branched polyurethane and obtains.
2. high-performance environment protection type TPE preservative film as claimed in claim 1, wherein, in described polyquaternium-chitosan-super branched polyurethane mixture, described polyquaternium is by dibenzyl bromine and Isosorbide-5-Nitrae-lupetazin 1:(0.8 ~ 0.99 in molar ratio) prepare.
3. as profit requires the high-performance environment protection type TPE preservative film as described in 1, wherein, described amino-terminated sulfonate polybenzimidazole prepolymer is 1:(0.8 ~ 0.98 by tetramine and sulfonation diacid in molar ratio) prepare.
4., as profit requires the high-performance environment protection type TPE preservative film as described in 3, wherein, described tetramine is selected from 3,3'-diaminobenzidine, 3,3', 4,4'-tetramino phenyl ether, 3,3', 4,4'-tetramino sulfobenzide, 3,3', 4,4'-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1, in 2,5,6-tetramino naphthalene any one or multiple.
5., as profit requires the high-performance environment protection type TPE preservative film as described in 3, wherein, described sulfonation diacid is selected from 2-
Any one or two kinds in sulfonic acid terephthalic acid and 4-sulfonic acid m-phthalic acid.
6. high-performance environment protection type TPE preservative film as claimed in claim 1, wherein, described processing aid is selected from
In lipid acid, soap, fatty acid amide and silicone material any one or multiple.
7. high-performance environment protection type TPE preservative film as claimed in claim 1, wherein, described one package stabilizer is selected from
In benzophenone, phosphorous acid esters, Hinered phenols and hindered amines material any one or multiple.
8. prepare the method for polyquaternium-chitosan-super branched polyurethane mixture as claimed in claim 1, comprising:
A () prepares polyquaternium modified chitosan:
In 100ml three-necked bottle, add chitosan 0.1mol and polyquaternium 0.01 ~ 0.2mol according to claim 2, after stirred at ambient temperature is even; Take the sodium hydroxide of 0.01 ~ 0.3mol and with after water dissolution, add said mixture, reacting after 10 ~ 24 hours at 30 ~ 60 DEG C, neutralize with Hydrogen bromide and after using ethanol repetitive scrubbing, suction filtration and dry must polyquaternium modified chitosan.
B () prepares hyperbranched:
Vulcabond and trivalent alcohol are dissolved in polar solvent respectively, obtain diisocyanate solution respectively
With trivalent alcohol solution, controlling its mass concentration is 5 ~ 30%; Wherein, vulcabond is isophorone diisocyanate, 4 ' 4-diphenylmethanediisocyanate, hexamethylene diisocyanate or 2,4 tolylene diisocyanates; Described trivalent alcohol is glycerol, TriMethylolPropane(TMP) or polyether-tribasic alcohol;
30 ~ 100 DEG C, under protective atmosphere, limit is stirred, and diisocyanate solution is added to trivalent alcohol molten
In liquid, wherein the mol ratio of the isocyanato of vulcabond and the hydroxyl of trivalent alcohol is 9:8 ~ 3:1; After vulcabond has added, reaction system insulation reaction 10 ~ 30h; Then in reaction system, add protective material, at 30 ~ 100 DEG C, continue reaction 5 ~ 10h;
After end, after underpressure distillation goes out solvent, dissolved by gained material through tetrahydrofuran (THF), sedimentation and after filtering in methyl alcohol, by its vacuum-drying 10 ~ 24h at 50 ~ 140 DEG C, obtains the super branched polyurethane containing isocyanato of purifying;
C () prepares polyquaternium-chitosan-super branched polyurethane mixture:
In 100ml three-necked bottle, add the polyquaternium modified chitosan 0.1 gram of above-mentioned synthesis, super branched polyurethane 0.2 ~ 2 gram and DMF 50ml, after stirred at ambient temperature is even; React after 10 ~ 24 hours at 30 ~ 60 DEG C, sedimentation and filtration in methyl alcohol, obtain polyquaternium-chitosan-super branched polyurethane mixture.
9. prepare the method for high-performance environment protection type TPE preservative film, comprise the steps:
Get the raw material described in any one of claim 1 ~ 7, use twin screw extruder granulation; Then, in plastic extrusion inflation film manufacturing machine, extrusion moulding obtains antistaling film;
Wherein, twin screw extruder each section of temperature, from charging opening, is followed successively by 180 ~ 200 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, 185 ~ 205 DEG C, head temperature 185 ~ 200 DEG C;
Thin film extruding machine host machine part temperature is for from charging opening, and be followed successively by 150 ~ 160 DEG C, 165 ~ 175 DEG C, 170 ~ 180 DEG C, 175 ~ 185 DEG C, 180 ~ 190 DEG C, head section temperature is 175 ~ 185 DEG C.
10. the method preparing high-performance environment protection type TPE preservative film of claim 9, also comprises:
The antistaling film obtained is immersed in polyphosphoric acid, keeps after 3 ~ 8 hours at 120 ~ 180 DEG C, be washed till neutral also vacuum-drying with deionized water and obtain preservative film crosslinked further.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070396A (en) * | 2007-06-21 | 2007-11-14 | 深圳职业技术学院 | Environment-protective SEBS fresh-preservation film and producing method thereof |
| CN101402718A (en) * | 2008-11-24 | 2009-04-08 | 中国人民解放军总后勤部军需装备研究所 | Process for producing material with equivalent heat-transfer performance of human body skin |
| CN102731954A (en) * | 2011-04-15 | 2012-10-17 | 烟台百特塑化制品有限公司 | Preparation method of SEBS nano saddle zipper preservative film bag |
| CN103668544A (en) * | 2013-12-11 | 2014-03-26 | 浙江华峰氨纶股份有限公司 | Polyurethane elastic fibers with multielement functionality and preparation method thereof |
| CN104817807A (en) * | 2015-04-21 | 2015-08-05 | 安徽雄亚塑胶科技有限公司 | Environment-friendly recyclable cross-linked TPE (thermoplastic elastomer) tourniquet and preparation method thereof |
| CN104830012A (en) * | 2015-05-12 | 2015-08-12 | 安徽雄亚塑胶科技有限公司 | High-performance TPE operating tablecloth and preparation method thereof |
-
2015
- 2015-11-18 CN CN201510795287.6A patent/CN105367973A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070396A (en) * | 2007-06-21 | 2007-11-14 | 深圳职业技术学院 | Environment-protective SEBS fresh-preservation film and producing method thereof |
| CN101402718A (en) * | 2008-11-24 | 2009-04-08 | 中国人民解放军总后勤部军需装备研究所 | Process for producing material with equivalent heat-transfer performance of human body skin |
| CN102731954A (en) * | 2011-04-15 | 2012-10-17 | 烟台百特塑化制品有限公司 | Preparation method of SEBS nano saddle zipper preservative film bag |
| CN103668544A (en) * | 2013-12-11 | 2014-03-26 | 浙江华峰氨纶股份有限公司 | Polyurethane elastic fibers with multielement functionality and preparation method thereof |
| CN104817807A (en) * | 2015-04-21 | 2015-08-05 | 安徽雄亚塑胶科技有限公司 | Environment-friendly recyclable cross-linked TPE (thermoplastic elastomer) tourniquet and preparation method thereof |
| CN104830012A (en) * | 2015-05-12 | 2015-08-12 | 安徽雄亚塑胶科技有限公司 | High-performance TPE operating tablecloth and preparation method thereof |
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| CN112538228A (en) * | 2020-12-04 | 2021-03-23 | 安徽强茗塑业科技有限公司 | Antibacterial ABS plastic and preparation method thereof |
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