CN107216439A - A kind of polyurethane-urea chitin copolymer and its preparation method and application - Google Patents
A kind of polyurethane-urea chitin copolymer and its preparation method and application Download PDFInfo
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- CN107216439A CN107216439A CN201710507853.8A CN201710507853A CN107216439A CN 107216439 A CN107216439 A CN 107216439A CN 201710507853 A CN201710507853 A CN 201710507853A CN 107216439 A CN107216439 A CN 107216439A
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- urea
- polyurethane
- chitosan
- performed polymer
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- 229920002101 Chitin Polymers 0.000 title claims abstract description 51
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003921 oil Substances 0.000 claims abstract description 21
- -1 degradability Substances 0.000 claims abstract description 20
- 239000002985 plastic film Substances 0.000 claims abstract description 9
- 229920006255 plastic film Polymers 0.000 claims abstract description 8
- 239000008157 edible vegetable oil Substances 0.000 claims abstract description 7
- 229920001661 Chitosan Polymers 0.000 claims description 63
- 229920000642 polymer Polymers 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- 229920001577 copolymer Polymers 0.000 claims description 29
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 22
- 239000012948 isocyanate Substances 0.000 claims description 15
- 150000002513 isocyanates Chemical class 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 4
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 4
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 4
- 229920002635 polyurethane Polymers 0.000 claims 3
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 238000007654 immersion Methods 0.000 abstract description 10
- 229920003023 plastic Polymers 0.000 abstract description 10
- 239000004033 plastic Substances 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004519 grease Substances 0.000 abstract description 5
- 230000008595 infiltration Effects 0.000 abstract description 5
- 238000001764 infiltration Methods 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 4
- 229920006238 degradable plastic Polymers 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920000578 graft copolymer Polymers 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001555 benzenes Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
It is long-chain polyurethane-urea that the present invention, which provides a kind of polyurethane-urea chitin copolymer, and its molecular weight is 20000 ~ 100000；With controlled degradation, water resistant, oily permeability, and for plastic film, the mechanical property after degradable plastic film immersion oil in the prior art is improved, so as to improve the security of plastic film.Its preparation methods steps are simple and direct, be easily controlled, and the molecular weight of each step is controlled by control parameter, so as to control the mechanical property of material, degradability, grease resistance.And it is difficult infiltration for edible oil, ink stamp-pad ink, antirust oil etc. applied to plastic package material is prepared.
Description
Technical field
The present invention relates to a kind of polyurethane-urea-chitin copolymer and its preparation method and application, belong to high polymer material
Technical field.
Background technology
At present, thermoplastic starch, PLA and aliphatic polyester are biodegradable plastics in three kinds of main environment.Poly- breast
Although sour intensity is suitable with general-purpose plastics, its poor heat resistance, fragility greatly, and one times more expensive than polyolefin of its price with
On, therefore limit its practical application in environmental organism decomposing material field；In order to improve the physical property of polylactic acid plastic
With processing characteristics, reduction price, many researchs have been done in the intermingling material field of starch/polylactic acid.For example Chinese patent is disclosed
Entitled " a kind of vinol/polylactic acid graft copolymer and its intermingling material with starch and their preparation side
Method, purposes " (Application No. 200610020448.5) discloses the blending of vinol/polylactic acid graft copolymer and starch
Material and the method for preparing vinol/polylactic acid graft copolymer, and graft copolymer and its intermingling material with starch
Purposes.Because the glass transition temperature and fusing point of the invention graft copolymer are larger apart, thus can completely it be given birth to as one kind
The thermoplastic raw material of thing degraded is used, and extends the application field of PLA；Add blending material obtained by starch/chitosan
Material not only greatly reduces cost, and also improves the biodegradation rate of graft copolymer；Graft copolymer and itself and shallow lake
The blend of powder/chitosan also has good processing characteristics and excellent mechanical performance, can especially be used directly to be blow molded into thin
Film.But the copolymer still haves the shortcomings that poor compatibility, degrade that uncontrollable, stability is poor, film forming is poor.
The security of plastic package material, the feature of environmental protection and Water-proof and oil-proof performance are most important, while current plastics package
It is primarily present following deficiency：1st, based on polyethylene, polypropylene material, non-degradable, and the feature of environmental protection is not enough；2nd, PLA material
Expect that controlled degradation is poor；3rd, the water resistant of polyurethane-urea, oily poor permeability, for edible oil, ink stamp-pad ink, antirust oil etc. easily
Infiltration.Therefore, how to provide one kind has controllable degradation property and the infiltrative polyurethane-urea of water resistant oil, solves above-mentioned plastics
The deficiency that packaging material has, as those skilled in the art's technical barrier urgently to be resolved hurrily.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of polyurethane-urea-chitosan copolymerization
Thing and its preparation method and application, the problems such as solving plastics package non-degradable, water resistant, oily poor permeability.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of polyurethane-urea-chitin copolymer, it is characterised in that its structural formula is as follows：
Further, the present invention also provides a kind of preparation method of polyurethane-urea-chitin copolymer, comprises the following steps：
Step 1：Small molecule glycol and Lanthanum Isopropoxide (PDO), lactide (LA) are reacted under stannous octoate effect,
Hydroxy-end capped performed polymer is prepared, mean molecule quantity is 1000~4000；The small molecule glycol is OH- (CH2) n-OH, its
Middle n=1~6；The reaction system is molten system；Reaction temperature is 140-145 DEG C, and reaction pressure is -0.096MPa, instead
It is 12-24h between seasonable；
Step 2：It is pre- that the performed polymer that step 1 is obtained reacts obtained polyurethane-urea with isocyanates under stannous octoate effect
Aggressiveness, the mean molecule quantity of the polyurethane-urea performed polymer is 8000~10000；Isocyanates and hydroxy-end capped performed polymer
Reaction system be solution system, the solution be benzene series solution；Reaction temperature is 70-75 DEG C；Reaction time is 10-14h；
Step 3：The polyurethane-urea performed polymer that step 2 is obtained and the chitosan and the isopropyl of small molecule diamines that are slowly dropped into
Alcoholic solution is reacted, and realizes the grafting of chitosan, while long-chain polyurethane-urea is obtained, it is final to be made as claimed in claim 1
Polyurethane-urea-chitin copolymer, its molecular weight is 20000~100000；The small molecule diamines is NH2-(CH2)n-NH2,
Wherein n=1~6, the chitosan is respectively low molecule amount and high molecular weight chitosan, and molecular weight is 5000~50000；
The reaction system of polyurethane-urea performed polymer and chitosan and small molecule diamines is solution system, and the solution is benzene series
Solution；Reaction temperature is 70-75 DEG C；Reaction temperature is 5 DEG C of temperature；Reaction time is 3-6h.
In the step 1, the mol ratio of small molecule glycol and lactide (LA) is 1:20~200；Lanthanum Isopropoxide
(PDO) it is 1 with the mol ratio of lactide (LA):1~10.
In the step 2, isocyanates includes any of difunctional isocyanates or trifunctional isocyanate；
Isocyanates consumption is guarantee NCO:OH mol ratios are 1.1-1.5:1.
In the step 3, the mol ratio of polyurethane-urea performed polymer and chitosan and small molecule diamines is guarantee NCO：NH2=
1：1~1.2, the mol ratio of chitosan and small molecule diamines is 1 in the reaction：1/5~10, it is ensured that the introduction volume of chitosan
In certain gradient.
The present invention also provides the application of the polyurethane-urea-chitin copolymer, for preparing plastic film.It is described
Polyurethane-urea-chitosan has controllable degradability, and degradability is on a declining curve with the reduction of PDO and LA mol ratios, described
Degradation time is 6~24 months.Polyurethane-urea-the chitosan has excellent oil resistivity, resistance in 6~24 months
Edible oil, antirust oil, printing-ink.
Compared with prior art, the present invention has the advantages that：
1st, polyurethane-urea-chitin copolymer of the present invention is long-chain polyurethane-urea, and its molecular weight is 20000~100000；
With degradability, water resistant, oily permeability, and degradation plastic in the prior art is improved for plastic film
The mechanical property of film, so as to improve the security of plastic film.
2nd, the preparation method of polyurethane-urea-chitin copolymer of the present invention, is realized by the ratio for adjusting reaction monomers：
(1) mechanical property of convenient control material, makes its mechanical property match with its application；(2) convenient control degradability, is solved
Degradable, the slow problem of aliphatic Degradation of Polymer Materials；(3) grease proofness of convenient control material, is solved existing
The problem of grease proofness that degredation plastic film is present in technology is poor, available for prepare plastic package material for edible oil,
Ink stamp-pad ink, antirust oil etc. are difficult infiltration.
3rd, the preparation method of polyurethane-urea-chitin copolymer of the present invention, step is simple and direct, be easily controlled, by controlling to join
Count to control the molecular weight of each step, so as to control the mechanical property of material, degradability, grease resistance.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of hydroxy-end capped performed polymer.
Fig. 2 is a kind of polyurethane-urea of the invention-chitin copolymer synthesis schematic diagram.
Fig. 3 is polyurethane-urea of the present invention-chitin copolymer infrared spectrogram.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of polyurethane-urea-chitosan of the present invention.
Fig. 5 is the immersion oil lab diagram of polyurethane-urea-chitosan film of the present invention.
Fig. 6 is the weight change figure of polyurethane-urea of the present invention-chitin copolymer film immersion oil experiment.
For the thermal multigraph of polyurethane-urea of the present invention-chitin copolymer film, (abscissa is temperature to Fig. 7, and ordinate is attached most importance to
Measure ratio).
Fig. 8 schemes for the SEM of polyurethane-urea of the present invention-chitin copolymer film.
Fig. 9 polyurethane-ureas-chitin copolymer film weightlessness figure.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.Now use 1~3 point of example
The sign of bright polyurethane-urea-chitosan synthesis and physical property and chemical property is not mentionleted alone.It should be noted that following embodiments
Described in technical characteristic or technical characteristic combination be not construed as it is isolated, they can be mutually combined from
And reach superior technique effect.
1 polyurethane-urea of embodiment-chitosan synthesis
Step 1：It is the synthetic route of hydroxy-end capped performed polymer referring to Fig. 1
Ethylene glycol (EG) from n=2 is small molecule glycol, with EG/ (PDO+LA)=1:200, PDO/LA=1:5 ratio
Example prepares hydroxy-end capped performed polymer, the number-average molecular weight 4000 of obtained performed polymer；The reaction system is molten mass
System；Reaction temperature is 140 DEG C, and reaction pressure is -0.096MPa, and the reaction time is 18h；
Step 2：It is polyurethane-urea-chitin copolymer synthetic route referring to Fig. 2
By the hydroxy-end capped performed polymer that molecular weight is 4000, the HDI containing double NCO is reacted, and prepares polyurethane-urea
Performed polymer, the HDI added content is, it is ensured that NCO/OH mol ratio is 1.1：1, obtained polyurethane-urea performed polymer
Number-average molecular weight is 12000；The reaction system of isocyanates and hydroxy-end capped performed polymer is solution system, and the solution is benzene
It is solution；Reaction temperature is 75 DEG C；Reaction time is 12h；
Step 3：The shell that the polyurethane-urea performed polymer for the NCO bases end-blocking for being 12000 by molecular weight is 10000 with molecular weight gathers
The aqueous isopropanol of sugar and n=4 butanediamine reacts jointly, it is ensured that NCO/NH2Ratio be 1:1.05；Simultaneously respectively with shell
The mol ratio of glycan/butanediamine is 1:2、1:1 and 1:0.5 ratio prepares polyurethane-urea-chitin copolymer, is made respectively
Copolymer 1,3 three kinds of copolymers of copolymer 2 and copolymer, its molecular weight is respectively 50000,38000,42000；Polyurethane-urea
The reaction system of performed polymer and chitosan and small molecule diamines is solution system, and the solution is benzene series solution；Reaction temperature is
5℃；Reaction time is 4h.
The structural formula of its polyurethane-urea-chitin copolymer is as follows：
2 polyurethane-ureas of embodiment-chitosan synthesis
Step 1：It is the synthetic route of hydroxy-end capped performed polymer referring to Fig. 1
1,6- hexylene glycols from n=4 are small molecule glycol, with hexylene glycol/(PDO+LA)=1:50；PDO/LA=1:
2.0 ratio prepares hydroxy-end capped performed polymer, the number-average molecular weight 2457 of obtained performed polymer；The reaction system is
Molten system；Reaction temperature is 140 DEG C, and reaction pressure is -0.096MPa, and the reaction time is 18h；
Step 2：It is polyurethane-urea-chitin copolymer synthetic route referring to Fig. 2
By the hydroxy-end capped performed polymer that molecular weight is 2457, the HDI containing double NCO is reacted, and prepares polyurethane-urea
Performed polymer, the HDI added content is, it is ensured that NCO/OH mol ratio is 1.3：1, obtained polyurethane-urea performed polymer
Number-average molecular weight is 7500；The reaction system of isocyanates and hydroxy-end capped performed polymer is solution system, and the solution is benzene
It is solution；Reaction temperature is 75 DEG C；Reaction time is 12h；
Step 3：The shell that the polyurethane-urea performed polymer for the NCO bases end-blocking for being 7500 by molecular weight is 10000 with molecular weight gathers
The aqueous isopropanol of sugar and n=6 hexamethylene diamine reacts jointly, it is ensured that NCO/NH2Ratio be 1:1.2；It is simultaneously poly- with shell respectively
The mol ratio of sugar/butanediamine is 1:7.5 ratios prepare polyurethane-urea-chitin copolymer, obtained polyurethane-urea-chitosan
Molecular weight be 90000 (but the polymer under the molecular weight has a certain proportion of crosslinking phenomena).
The reaction system of polyurethane-urea performed polymer and chitosan and small molecule diamines is solution system, and the solution is benzene series
Solution；Reaction temperature is 5 DEG C；Reaction time is 4h.
3 polyurethane-ureas of embodiment-chitosan synthesis (reaction condition be the same as Example 1)
Step 1：It is the synthetic route of hydroxy-end capped performed polymer referring to Fig. 1
Ethylene glycol from n=2 is small molecule glycol, with EG/ (PDO+LA)=1:20；PDO/LA=1:4.5 ratio
Prepare hydroxy-end capped performed polymer, the number-average molecular weight 1680 of obtained performed polymer；
Step 2：It is polyurethane-urea-chitin copolymer synthetic route referring to Fig. 2
Molecular weight is reacted for 1680 hydroxy-end capped performed polymer with the TDI containing double NCO, polyurethane-urea is prepared
Performed polymer, the TDI added content is, it is ensured that NCO/OH mol ratio is 1.1：1, obtained polyurethane-urea performed polymer
Number-average molecular weight is 5000；
Step 3：The chitosan that the polyurethane-urea performed polymer for the NCO bases end-blocking for being 5000 by molecular weight is 5000 with molecular weight
And the aqueous isopropanol of n=4 butanediamine reacts jointly, it is ensured that NCO/NH2Ratio be 1:1.1；It is simultaneously poly- with shell respectively
The mol ratio of sugar/butanediamine is 1:5 ratios prepare polyurethane-urea-chitin copolymer, obtained polyurethane-urea-chitosan
Molecular weight is 65000.
The preparation method of the polyurethane-urea-chitin copolymer, comprises the following steps：
4 polyurethane-ureas of embodiment-chitin copolymer chemical constitution is characterized
This example carries out preliminary characterization using infrared spectrum, NMR spectrum to its chemical constitution, has primarily determined that poly-
The synthesis of urethane urea-chitosan, Fig. 3 and Fig. 4 are respectively the infrared spectrum and proton nmr spectra of copolymer 2.And using polygonal
The method of degree laser light scattering instrument (U.S., Wyatt technology companys) determines the weight average molecular weight of copolymer 1~3, is specifically shown in
Example 1.
Specific experimental method is as described below：
(1) infrared absorption spectrum analysis
SMPUU samples are dissolved in after chloroform, the solution-cast film forming on transparent KBr windows treats that solvent volatilizees completely
Use Spectrum GX types infrared afterwards and microscopic system (U.S., Perkin Elmer companies) record polyurethane-urea-chitosan 2
In 400-4000cm-1Infrared absorption spectroscopy.
(2) hydrogen nuclear magnetic resonance analysis of spectrum
With deuterochloroform CDCl3(Fluka Chemica, 99.8%) it is solvent, tetramethylsilane that heavy hydrogen content is not less than
(TMS) it is internal standard, polyurethane-urea-chitosan is detected with AV-500 types NMR spectrometer with superconducting magnet (Switzerland, Bruker companies)
Copolymer 21H NMR spectras.
(3) measure of weight average molecular weight：SMPUU samples are dissolved in after chromatographically pure THF, using detection polyurethane-urea-shell
Number-average molecular weight (the M of glycan 2n) and the feature such as molecular weight distribution (PD).The splitter of instrument：Agilent 1100HPLC
Columns；Mobile phase：Chromatographically pure THF；Flow velocity：1mL/min.
Described in example 1, respectively using the mol ratio of chitosan/butanediamine as 1:2、1:1、1:0.5 ratio prepares poly- ammonia
Ester urea-chitin copolymer, is made copolymer 1, copolymer 2, copolymer 3 respectively, and the molecular weight of three kinds of copolymers is respectively
50000th, 38000,42000, illustrate shadow of the process by two factors of polyurethane-urea performed polymer and chitosan/diamine reactant
Ring：Contain NH2Chitosan and diamines reactivity and the molecular weight of chitosan.
The infrared spectrum of Fig. 3 polyurethane-urea-chitin copolymer 2 is compareed with original polyurethane-urea infrared spectrum, it is seen that
Two characteristic peaks：Peak is narrower at 3300, characteristic peak is more sharp at 866, it can thus be appreciated that chitosan is successfully introduced into.
The proton nmr spectra of Fig. 4 polyurethane-urea-chitin copolymer 2 and the proton nmr spectra of original polyurethane-urea
Compare, it is seen that add the characteristic peak near 2.2 and 3.6, according to the literature CH of this feature peak on chitosan ring2
Characteristic peak, further demonstrate being successfully introduced into for chitosan.
5 polyurethane-ureas of embodiment-chitosan surface topography is characterized
This example carries out SEM experiments to polyurethane-urea-chitin copolymer 1~3, first to copolymerization by the way of metal spraying
Thing carries out surface preparation, then carries out SEM detections, from Fig. 8 results, with the copolymer that improves of chitosan content
Surface flatness is reduced, and especially copolymer 3 is detected from SEM, obvious phase separation is there is, to its mechanical property
It there is certain influence.
6 polyurethane-ureas of embodiment-chitin copolymer physical property is characterized
The immersion oil experiment of immersion oil measuring polyurethane-urea-chitin copolymer 1~3 is respectively adopted, in immersion oil 14 days
Determine the mechanical stretch performance and peel strength (heat-sealing that sufficient intensity is carried out before immersion oil) of three kinds of copolymers respectively afterwards；
Thermogravimetric analysis has been carried out to polyurethane-urea-chitosan 2 in addition；
Specific experimental method is as described below：
(1) polyurethane-urea-chitin copolymer immersion oil experiment
As shown in figure 5, at 155 DEG C, 100KPa is sealed under conditions of 5s, the modeling after heat-sealing to copolymer 1~3
Load a certain amount of edible oil in pocket and carry out immersion test, the time continues 30 days.Period respectively at the 7th day, the 14th day,
21 days, sampling in the 30th day carried out the measure of gross weight.From Fig. 6 data, with the increase of chitosan content, thin polymer film
Oil-resistant characteristic significantly improve, copolymer 2 and 3 during testing in, do not occur the change of oil mass substantially.
(2) polyurethane-urea-chitin copolymer mechanical property and stripping performance experiment
After polyurethane-urea-chitosan polybag is carried out into immersion test 14 days, strip (long 80mm, wide 10mm) is made,
Mechanical stretch experiment and peel test are carried out on intelligent Experiments of Machanics stretching-machine, concrete outcome is shown in Table 1, can by the result of table 1
See, with the raising of chitosan content, the grease resistance of polymer is improved, and the mechanical stretch performance after soaking 14 days is far above poly-
Urethane urea and the low copolymer 1 of chitosan content and 2.In addition, after the soak test of 14 days, the glass of all polymer
Property be satisfied by Standard, therefore copolymer has the security used.
Mechanical property and heat-sealing stripping performance after 1. polyurethane-ureas of table-chitin copolymer film soaks 14 days
(3) polyurethane-urea-chitosan thermogravimetric analysis experiment
It is measured using the differential thermal analyzer of Beijing Optical Instrument Factory, sample dosage is 12mg, and sample is from room temperature with 10
DEG C/min speed rises to 550 DEG C.Thermal gravimetric analysis results are as shown in fig. 7, Fig. 7 show polyurethane-urea-chitin copolymer 2
Thermogravimetric analysis figure, the figure is more smooth as seen from the figure, have no obvious multistage weightless visible polyurethane-urea-chitosan into
Work(is synthesized, wherein being substantially not present monomeric substance.
7 polyurethane-ureas of embodiment-chitin copolymer thing degradation property is characterized
Such as embodiment 1, change the ratio between chitosan and small molecule diamines, the poly- ammonia of three kinds of molecular weight is obtained respectively
Ester urea-chitosan, illustrates the molecular weight of polyurethane-urea-chitosan, may by small molecule diamines content and chitosan molecule
Measure the influence of two factors, and be mainly reflected in structure chitosan branched structure not ibid.
Embodiment 1 is under conditions of step 1 and 2 all sames, the poly- ammonia that step 3 blocks the NCO bases that molecular weight is 12000
Ester urea performed polymer is that 10000 chitosan and n=4 butanediamine react jointly with molecular weight, it is ensured that NCO/NH2Ratio be
1:1.05；Simultaneously respectively using the mol ratio of chitosan/butanediamine as 1:2、1:1 and 1:0.5 ratio prepares polyurethane-urea-shell and gathered
Sugar copolymer, is made copolymer 1,3 three kinds of copolymers of copolymer 2 and copolymer respectively, its molecular weight is respectively 50000,
38000、 42000。
External degradation experiment, experiment condition are carried out to copolymer 1-3：PBS；Degradation temperature：25℃；Aseptic condition
It is lower to stand；Duration of the reaction 180 days；Now take 30 respectively, 60,90,120,150,180 days when 6 data to copolymer 1-3
Degraded situation contrasted, see Fig. 9.From Fig. 9 results, the degraded of the introducing of chitosan to polyurethane-urea has regulation and control
Effect.
From above-described embodiment, polyurethane-urea-chitin copolymer that the present invention is provided can solve to use in the prior art
In the shortcoming that the security of plastic film is poor, the uncontrollable, oil preventing performance of degraded is poor, preparation technology of the invention is simple, institute
Polyurethane-urea-chitin copolymer of preparation controllable can be explained, and with water resistant oil infiltration, for preparing plastics package material
Material is difficult infiltration for edible oil, ink stamp-pad ink, antirust oil etc..
Above-mentioned detailed description is illustrated for the possible embodiments of invention, and the embodiment simultaneously is not used to limit this hair
In bright the scope of the claims, all equivalence enforcements or change without departing from the present invention, the scope of the claims that should be contained in the present invention.
In addition, those skilled in the art can also the claims in the present invention scope of disclosure and spirit in do other forms with
Various modifications, addition and replacement in details.Certainly, these various modifications made according to present invention spirit, addition and replacements
Deng change, it should all be included within scope of the present invention.
Claims (9)
1. a kind of polyurethane-urea-chitin copolymer, it is characterised in that its structural formula is as follows：
2. a kind of preparation method of polyurethane-urea-chitin copolymer, it is characterised in that comprise the following steps：
Step 1：Small molecule glycol and Lanthanum Isopropoxide (PDO), lactide (LA) are reacted under stannous octoate effect, prepared
Hydroxy-end capped performed polymer, mean molecule quantity is 1000~4000；The small molecule glycol is OH- (CH2) n-OH, wherein n=1
~6；The reaction system is molten system；Reaction temperature is 140-145 DEG C, and reaction pressure is -0.096MPa, and the reaction time is
12-24h；
Step 2：The performed polymer that step 1 is obtained reacts with isocyanates under stannous octoate effect is made polyurethane-urea pre-polymerization
Body, the mean molecule quantity of the polyurethane-urea performed polymer is 8000~10000；Isocyanates is anti-with hydroxy-end capped performed polymer
It is solution system to answer system, and the solution is benzene series solution；Reaction temperature is 70-75 DEG C；Reaction time is 10-14h；
Step 3：The polyurethane-urea performed polymer that step 2 is obtained and the chitosan and the isopropanol of small molecule diamines that are slowly dropped into are molten
Liquid is reacted, and realizes the grafting of chitosan, while long-chain polyurethane-urea is obtained, it is final that poly- ammonia as claimed in claim 1 is made
Ester urea-chitin copolymer, its molecular weight is 20000~100000；The small molecule diamines is NH2-(CH2)n-NH2, wherein n
=1~6, the chitosan is respectively low molecule amount and high molecular weight chitosan, and molecular weight is 5000~50000；
The reaction system of polyurethane-urea performed polymer and chitosan and small molecule diamines is solution system, and the solution is that benzene series is molten
Liquid；Reaction temperature is 70-75 DEG C；Reaction temperature is 5 DEG C of temperature；Reaction time is 3-6h.
3. the preparation method of polyurethane-urea-chitin copolymer according to claim 2, it is characterised in that the step 1
In, the mol ratio of small molecule glycol and lactide (LA) is 1:20~200；Lanthanum Isopropoxide (PDO) and lactide (LA)
Mol ratio is 1:1~10.
4. the preparation method of polyurethane-urea-chitin copolymer according to claim 2, it is characterised in that the step 2
In, isocyanates includes any of difunctional isocyanates or trifunctional isocyanate；Isocyanates consumption is guarantor
Demonstrate,prove NCO:OH mol ratios are 1.1-1.5:1.
5. the preparation method of polyurethane-urea-chitin copolymer according to claim 2, it is characterised in that the step 3
In, the mol ratio of polyurethane-urea performed polymer and chitosan and small molecule diamines is guarantee NCO：NH2=1：1~1.2, the reaction
The mol ratio of middle chitosan and small molecule diamines is 1：1/5~10, it is ensured that the introduction volume of chitosan is in certain gradient.
6. a kind of preparation method of polyurethane-urea-chitin copolymer, it is characterised in that comprise the following steps：
Step 1：Ethylene glycol (EG) from n=2 is small molecule glycol, with EG/ (PDO+LA)=1:200, PDO/LA=1:5
Ratio prepares hydroxy-end capped performed polymer, the number-average molecular weight 4000 of obtained performed polymer；The reaction system is molten mass
System；Reaction temperature is 140-145 DEG C, and reaction pressure is -0.096MPa, and the reaction time is 12-24h；
Step 2：By the hydroxy-end capped performed polymer and n=6 that molecular weight is 4000, the HDI containing double NCO is reacted, and is prepared
Polyurethane-urea performed polymer, the HDI added content is, it is ensured that NCO/OH mol ratio is 1.1：1, obtained polyurethane-urea is pre-
The number-average molecular weight of aggressiveness is 12000；The reaction system of isocyanates and hydroxy-end capped performed polymer is solution system, described molten
Liquid is benzene series solution；Reaction temperature is 70-75 DEG C；Reaction time is 12h；
Step 3：Chitosan that polyurethane-urea performed polymer and the molecular weight for the NCO bases end-blocking for being 12000 by molecular weight are 10000 and
N=4 butanediamine reacts jointly, it is ensured that NCO/NH2 ratio is 1:1.05；Simultaneously respectively with mole of chitosan/butanediamine
Than for 1:2、1:1 and 1:0.5 ratio prepares polyurethane-urea-chitin copolymer, and copolymer 1, copolymer 2 are made respectively and is total to
3 three kinds of copolymers of polymers, its molecular weight is respectively 50000,38000,42000；
The reaction system of polyurethane-urea performed polymer and chitosan and small molecule diamines is solution system, and the solution is that benzene series is molten
Liquid；Reaction temperature is 70-75 DEG C；Reaction temperature is 5 DEG C；Reaction time 4h.
7. a kind of application of polyurethane-urea-chitin copolymer, it is characterised in that the polyurethane as described in claim 1-6 is any
Urea-chitin copolymer is used to prepare plastic film.
8. a kind of application of polyurethane-urea-chitin copolymer, it is characterised in that the polyurethane as described in claim 1-6 is any
Urea-chitosan has controllable degradability, and degradability is on a declining curve with the reduction of PDO and LA mol ratios, during the degraded
Between be 6~24 months.
9. a kind of application of polyurethane-urea-chitin copolymer, it is characterised in that the polyurethane as described in claim 1-6 is any
Urea-chitosan has excellent oil resistivity, resistance to edible oil, antirust oil, printing-ink in 6~24 months.
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