CN107312322A - A kind of biodegradable thermoplastic method for preparing polyurethane elastic body - Google Patents
A kind of biodegradable thermoplastic method for preparing polyurethane elastic body Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
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- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical Kinetics & Catalysis (AREA)
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- Biological Depolymerization Polymers (AREA)
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Abstract
The present invention relates to a kind of biodegradable thermoplastic method for preparing polyurethane elastic body, concretely comprise the following steps：PLA and polycaprolactone glycol mixed melting are obtained into polyol component, catalyst and mixing diisocyanate is added dropwise, reaction obtains base polyurethane prepolymer for use as, gained performed polymer is mixed to be well mixed after material and is laid in teflon cloth with chain extender stirring, after be placed in vacuum drying oven, material is crushed after being taken out after 2 24h, into double screw extruder extrusion reaction, again by natural macromolecular, extruder is added after inorganic nano-particle is well mixed, granulated through underwater pelletizer, vacuum post curing, and removal moisture drying to moisture is less than 300ppm, prepare biodegradable thermoplastic polyurethane elastomer.The TPUE prepared using the inventive method has preferable biocompatibility and biodegradability.
Description
Technical field
The present invention relates to macromolecule material preparation area, and in particular to a kind of biodegradable thermoplastic polyurethane elastomer
Preparation method.
Background technology
TPUE is by the oligomer polyols such as the alkene such as polyethers, polyester or polyolefin and isocyanates
And a kind of polymer with carbamate constitutional repeating unit of glycol or Diamines chain extender progressively addition polymerization,
The characteristic of plastics and rubber is had concurrently, with excellent wearability, chemical resistance, oil resistivity and strong adhesive force, while having low
Warm curing performance and high-decoration energy.In recent years, using organosilicon, Organic fluoride and the modified modified polyurethane of nano structural material
Research report it is more, often show as ultra-low surface energy, chemically stable by modified elastomer and refuse oily water repellent etc., with wide
Wealthy application and development prospect.
As the purposes that polyurethane is developed is more and more, its consumption figure is also increasing.For machinery, communications and transportation,
Light industry, electrical package and insulation material and for automobile, the polyurethane in the field such as upholstery is required can be biodegradable.With can
It is that raw material prepares biodegradable polyurethane material to regenerate natural plant resource, can not only solve waste polyurethane material to environment
The problem of pollution, and it is useless to decrease the dependence to increasingly exhausted oil product, particularly agriculture and forestry by-product and agricultural
Gurry it is abundant
In this way, not only reduce the cost of material of polyurethane, but also improve agriculture and forestry by-product and agriculture and forestry organic waste material
Use value.In addition, medically, because polyurethane has good biocompatibility and antithrombotic, polyurethane can be extensive
Capsule applied to manufacture of intraocular internal organs such as artificial bone, artificial skin, suture and slow releasing pharmaceutical.Therefore, such biology can
Degradable polyurethane material will have very vast potential for future development.In the high polymer material selected by medical domain than industrial
Requirement it is much higher, especially to be implanted into human body material requirements it is higher, specific requirement is：Stable chemical performance；Histocompatbility
It is good；Non-carcinogenesis；Resistance to biological aging；It is amenable to various disinfecting process and consistency；Moulding processability is good.At present, polyurethane
The bioactivity of elastomer not enough, has significant limitation, so needing to prepare a kind of bioactivity in the application of medical domain
High polyurethane elastomer material, to meet medical domain to high molecular demand.
Natural macromolecular includes chitosan, hyaluronic acid, soybean protein, cellulose etc., with good biocompatibility,
It is biodegradable in human body, have no toxic side effect, wide material sources, bioactivity is high, therefore it is more common in biological medicine, health care food
In terms of product.But the mechanical performance of natural macromolecular, resistance to biological aging ability and moulding processability are substantially not enough.So being badly in need of
A kind of method, new polyurethane material is prepared using natural macromolecular, makes material except meeting the basic of bio-medical material
It is required that outside, the feature with the good bioactivity of natural macromolecular and a variety of excellent biological functions, while having poly- ammonia
The advantage of the resistance to biological aging of ester elastomer, the good, easy processing of mechanical property etc..
The content of the invention
It is an object of the invention to provide a kind of biodegradable thermoplastic method for preparing polyurethane elastic body, to solve
The problem of bioactivity of TPUE certainly of the prior art is not enough.
The invention provides a kind of biodegradable thermoplastic method for preparing polyurethane elastic body, step is as follows：
1) PLA and polycaprolactone glycol are added in there-necked flask, are placed in 50-120 DEG C of electric heating cover, stirring is extremely
The complete molten condition of reactant, obtains polyol component；Then, therefrom one is evacuated to after -0.01~-0.1MPa, 3-6h
It is 10-40Pa that bottleneck, which is filled with nitrogen to pressure, and catalyst is added dropwise, and it is (0.9-1.1) to add with polyol component mass ratio:1
Diisocyanate is mixed, 1-3h is reacted at 90 DEG C, obtains base polyurethane prepolymer for use as；
The mass ratio of the PLA and polycaprolactone is (1:5)-(5:1)；
One bottleneck of the there-necked flask is equipped with condenser pipe and thermometer, and another bottleneck is equipped with mechanical agitation rod, the machinery
Connected between stirring rod and glass stirring sleeve with vacuum rubber pipe；
2) by step 1 under nitrogen protection) to be warming up to 60-120 DEG C be 100 in mass ratio with chain extender group to gained performed polymer：
(8~12) mix more than 10s in the case where rotating speed is 5000~6000rpm mixing speeds, obtain well mixed material；
3) discharge：By step 2) resulting material is first cooled to about 60 DEG C, then stops stirring, stops nitrogen protection, by thing
Material be laid in 2mm or so in teflon cloth, after be placed in 90-130 DEG C of vacuum drying oven, after 2-24h take out after will
Material is crushed, into double screw extruder extrusion reaction, then by natural macromolecular, inorganic nano-particle it is well mixed after add and squeeze
Go out machine, granulated through underwater pelletizer, vacuum post curing, and removal moisture drying to moisture is less than 300ppm, prepares and biological can drop
Solve TPUE.
Further, the PLA, number-average molecular weight is 200~4000, described polycaprolactone glycol, the equal molecule of number
Measure as 500~4000.
Further, described catalyst is derived from metatitanic acid methyl esters, tetraethyl titanate, titanium propanolate, butyl titanate, two tin octoates
And one or both of dibutyl tin laurate mixture.
Further, described mixing diisocyanate is derived from toluene di-isocyanate(TDI), IPDI, six
Methylene diisocyanate, to phenyl diisocyanate, hexamethylene diisocyanate, 4,4- methyl diphenylene diisocyanates
In two or more mixture.
Further, described chain extender is derived from BDO, 2- methyl butanediol, 4- ethyls heptandiol and 3- methyl
The mixture of one or both of hexylene glycol.
Further, described natural macromolecular is derived from one kind in cellulose, starch, lignin.
Further, the number-average molecular weight of described natural macromolecular is 2 × 105~5 × 105。
Further, the mass ratio of the natural macromolecular and base polyurethane prepolymer for use as is (0.9:1)-(1.2:1) it is, inorganic
The mass ratio of nano-particle and base polyurethane prepolymer for use as is (0.01-0.1):1.
Further, the inorganic nano-particle is Nano-meter SiO_22、TiO2、Al2O3、CaCO3One kind in particle.
Beneficial effect using the invention described above technical scheme is：The thermoplastic polyurethane bullet prepared using the inventive method
Property body has good bioactivity, specific as follows：
(1) it is different with two using polyol component of the fully biodegradable polymer as polyurethane in the inventive method
Polyisocyanate reactant synthesizes nontoxic, safe, bioabsorbable and biodegradable polyurethane elastomer, while and large biological molecule
It is blended, with preferable biocompatibility and biodegradability；
(2) advantage of each isocyanates can be integrated using mixing isocyanates in the inventive method, can be according to the physical property of product
To select used isocyanates species；
(3) in the inventive method use nano-particle, nano material have skin effect, small-size effect, optical effect,
The special natures such as quantum size effect, can make material obtain new function, and such as granularity enters after nanoscale, and material surface is lived
Property increasing for center can improve its chemical catalysis and light-catalysed respond, in the presence of ultraviolet and oxygen to precoat from
Secondary chemical bonds can occur for the functional group of cleaning capacity, Active sites and film forming matter, greatly increase the rigidity of coating
And intensity, so as to improve the scratch resistance of coating, the nano-material surface of high surface energy by modification can obtain simultaneously hydrophobic and
Hate the characteristic of oil；
(4) natural macromolecular is used in the inventive method, its surface contains substantial amounts of hydroxyl and amino, with polyurethane have compared with
Strong hydrogen bond action, both can improve the biodegradable of polyurethane after being blended.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described, it is clear that described embodiment is a part of embodiment of the invention, rather than
Whole embodiments.
Embodiment 1
1) it is 1 that mass ratio is added in 1L there-necked flasks:1 polylactic acid diol and polyethylene glycol mixture 500g, a bottleneck
Condenser pipe and thermometer are filled, another bottleneck installation tool stirring rod is connected between stirring rod and glass stirring sleeve with vacuum rubber pipe,
And vacuum silicon grease lubrication and seal is coated, it is subsequently placed in 50-120 DEG C of electric heating cover, stirs to the complete molten condition of reactant,
It is used as polyol component；- 0.1MPa is evacuated to, a bottleneck is filled with holding 10-40Pa nitrogen protections, drop therefrom after 3 hours
Plus metatitanic acid methyl esters, it is 0.9 to add with polyol quality ratio:1 toluene di-isocyanate(TDI) and IPDI (both
Mass ratio is 1:1), reacted 2 hours at 90 DEG C, obtain base polyurethane prepolymer for use as；
2) above-mentioned product is warming up to 80 DEG C under nitrogen protection, be added dropwise BDO (prepolymer and BDO
Mass ratio is 100:10) it is used for blocked with polymer, mixes 15s in the case where rotating speed is 5000~6000rpm mixing speeds, must mix
Even material；
3) about 60 DEG C are cooled to, then stops stirring, stops nitrogen protection, product is laid in teflon cloth
2mm or so, after be placed in 100 DEG C of vacuum drying oven, taken out after 6h and crush material, added and the matter of base polyurethane prepolymer for use as
Amount is than being 0.9：(molecular weight is 3.56 × 10 to 1 starch5) with the mass ratio of base polyurethane prepolymer for use as it is 0.02:1 nano-TiO2Enter
Enter double screw extruder extrusion reaction, then by natural macromolecular, inorganic nano-particle it is well mixed after add extruder, through under water
Pelleter is granulated, vacuum post curing, and removal moisture drying to moisture is less than 300ppm, prepares the poly- ammonia of biodegradable thermoplastic
Ester elastomer.
Embodiment 2
1) it is 1 that mass ratio is added in 1L there-necked flasks:3 polylactic acid diol and polyethylene glycol mixture 500g, a bottleneck
Condenser pipe and thermometer are filled, another bottleneck installation tool stirring rod is connected between stirring rod and glass stirring sleeve with vacuum rubber pipe,
And vacuum silicon grease lubrication and seal is coated, it is subsequently placed in 50-120 DEG C of electric heating cover, stirs to the complete molten condition of reactant,
As polyol component, -0.01~-0.1MPa is evacuated to, a bottleneck is filled with holding 10-40Pa nitrogen therefrom after 3 hours
Protection, is added dropwise metatitanic acid methyl esters, and it is 0.9 to add with polyol quality ratio:1 toluene di-isocyanate(TDI) and isophorone diisocyanate
(both mass ratios are 1 to ester:1), reacted 2 hours at 90 DEG C, obtain base polyurethane prepolymer for use as；
2) above-mentioned product is warming up to 90 DEG C under nitrogen protection, 2- methyl butanediol (prepolymer and 2- methyl fourth two is added dropwise
The mass ratio of alcohol is 100:8) it is used for blocked with polymer, mixes 18s in the case where rotating speed is 5000~6000rpm mixing speeds, obtain mixed
Close homogeneous material；
3) about 60 DEG C are cooled to, then stops stirring, stops nitrogen protection, product is laid in teflon cloth
2mm or so, after be placed in 110 DEG C of vacuum drying oven, take out broken after 6h, add and the mass ratio of base polyurethane prepolymer for use as is
0.9：(molecular weight is 4.02 × 10 to 1 cellulose5) and with the mass ratio of base polyurethane prepolymer for use as be 0.01:1 nano-TiO2Into
Double screw extruder extrusion reaction, then by natural macromolecular, inorganic nano-particle it is well mixed after add extruder, through cutting under water
Grain machine granulation, vacuum post curing, and removal moisture drying to moisture is less than 300ppm, prepares biodegradable thermoplastic polyurethane
Elastomer.
Embodiment 3
1) it is 3 that mass ratio is added in 1L there-necked flasks:1 PLA and polyethylene glycol mixture 500g, a bottleneck fills cold
Solidifying pipe and thermometer, another bottleneck installation tool stirring rod, are connected, and apply between stirring rod and glass stirring sleeve with vacuum rubber pipe
Vacuum silicon grease lubrication and seal is covered, is subsequently placed in 50-120 DEG C of electric heating cover, stirring to the complete molten condition of reactant, as
Polyol component, is evacuated to -0.01~-0.1MPa, and a bottleneck is filled with holding 10-40Pa nitrogen protections therefrom after 3 hours,
Titanium propanolate is added dropwise, it is 1.1 to add with polyol quality ratio:1 toluene di-isocyanate(TDI) and IPDI (two
Person's mass ratio is 1:1), reacted 2 hours at 90 DEG C, obtain base polyurethane prepolymer for use as；
2) above-mentioned product is warming up to 95 DEG C under nitrogen protection, 4- ethyls heptandiol (prepolymer and 4- ethyls heptan two is added dropwise
The mass ratio of alcohol is 100:12) it is used for blocked with polymer, mixes 18s in the case where rotating speed is 5000~6000rpm mixing speeds, obtain mixed
Close homogeneous material；
3) about 60 DEG C are cooled to, then stops stirring, stops nitrogen protection, product is laid in teflon cloth
2mm or so, after be placed in 115 DEG C of vacuum drying oven, take out broken after 6h, add and the mass ratio of base polyurethane prepolymer for use as is
0.9：(molecular weight is 3.56 × 10 to 1 cellulose5) and with the mass ratio of base polyurethane prepolymer for use as be 0.05:1 Nano-meter CaCO33Enter
Enter double screw extruder extrusion reaction, then by natural macromolecular, inorganic nano-particle it is well mixed after add extruder, through under water
Pelleter is granulated, vacuum post curing, and removal moisture drying to moisture is less than 300ppm, prepares the poly- ammonia of biodegradable thermoplastic
Ester elastomer.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (9)
1. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body, it is characterised in that step is as follows：
1) PLA and polycaprolactone glycol are added in there-necked flask, are placed in 50-120 DEG C of electric heating cover, stirring to reaction
The complete molten condition of thing, obtains polyol component；Then, a bottleneck therefrom is evacuated to after -0.01~-0.1MPa, 3-6h
It is 10-40Pa to be filled with nitrogen to pressure, and catalyst is added dropwise, and it is (0.9-1.1) to add with polyol component mass ratio:1 mixing
Diisocyanate, reacts 1-3h at 90 DEG C, obtains base polyurethane prepolymer for use as；
The mass ratio of the PLA and polycaprolactone is (1:5)-(5:1)；
One bottleneck of the there-necked flask is equipped with condenser pipe and thermometer, and another bottleneck is equipped with mechanical agitation rod, the mechanical agitation
Connected between rod and glass stirring sleeve with vacuum rubber pipe；
2) by step 1 under nitrogen protection) to be warming up to 60-120 DEG C be 100 in mass ratio with chain extender group to gained performed polymer：(8~
12) more than 10s is mixed in the case where rotating speed is 5000~6000rpm mixing speeds, obtains well mixed material；
3) discharge：By step 2) resulting material is first cooled to about 60 DEG C, then stops stirring, and stop nitrogen protection, material is put down
Be laid on 2mm or so in teflon cloth, after be placed in 90-130 DEG C of vacuum drying oven, by material after being taken out after 2-24h
It is broken, into double screw extruder extrusion reaction, then by natural macromolecular, inorganic nano-particle it is well mixed after add and extrude
Machine, is granulated through underwater pelletizer, vacuum post curing, and removal moisture drying to moisture is less than 300ppm, prepares biodegradable
TPUE.
2. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In the PLA, number-average molecular weight is 200~4000, described polycaprolactone glycol, and number-average molecular weight is 500~4000.
3. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In described catalyst is derived from metatitanic acid methyl esters, tetraethyl titanate, titanium propanolate, butyl titanate, two tin octoates and tin dilaurate two
One or both of butyl tin mixture.
4. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In described mixing diisocyanate is derived from toluene di-isocyanate(TDI), IPDI, the isocyanic acid of hexa-methylene two
Ester, to two or more mixed in phenyl diisocyanate, hexamethylene diisocyanate, 4,4- methyl diphenylene diisocyanates
Compound.
5. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In：Described chain extender is derived from one kind in BDO, 2- methyl butanediol, 4- ethyls heptandiol and 3- methyl hexylene glycols
Or two kinds of mixture.
6. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In described natural macromolecular is derived from one kind in cellulose, starch, lignin.
7. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In the number-average molecular weight of described natural macromolecular is 2 × 105~5 × 105。
8. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In the mass ratio of the natural macromolecular and base polyurethane prepolymer for use as is (0.9:1)-(1.2:1), inorganic nano-particle and poly- ammonia
The mass ratio of ester performed polymer is (0.01-0.1):1.
9. a kind of biodegradable thermoplastic method for preparing polyurethane elastic body according to claim 1, its feature exists
In the inorganic nano-particle is Nano-meter SiO_22、TiO2、Al2O3、CaCO3One kind in particle.
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| CN201710519346.6A CN107312322A (en) | 2017-06-30 | 2017-06-30 | A kind of biodegradable thermoplastic method for preparing polyurethane elastic body |
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| CN201710519346.6A CN107312322A (en) | 2017-06-30 | 2017-06-30 | A kind of biodegradable thermoplastic method for preparing polyurethane elastic body |
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| CN201710519346.6A Pending CN107312322A (en) | 2017-06-30 | 2017-06-30 | A kind of biodegradable thermoplastic method for preparing polyurethane elastic body |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610618A (en) * | 2018-04-17 | 2018-10-02 | 杨建军 | A kind of degradable plastic film and preparation method thereof |
| CN109694494A (en) * | 2018-12-21 | 2019-04-30 | 山东一诺威聚氨酯股份有限公司 | Biodegradable thermoplastic polyurethane elastomer expanded bead and preparation method thereof |
| CN110790889A (en) * | 2019-11-20 | 2020-02-14 | 苏州市雄林新材料科技有限公司 | Polarity-controllable TPU film and preparation method thereof |
| CN110903452A (en) * | 2019-11-22 | 2020-03-24 | 广州睿特新材料科技有限公司 | Preparation method of lactic acid copolymer with high relative molecular mass |
| CN115260433A (en) * | 2022-06-24 | 2022-11-01 | 中国科学院宁波材料技术与工程研究所 | Bio-based high-damping thermoplastic polyurethane elastomer material and preparation method and application thereof |
| CN117510791A (en) * | 2023-12-29 | 2024-02-06 | 山东一诺威聚氨酯股份有限公司 | Biodegradable bio-based thermoplastic polyurethane elastomer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009067923A (en) * | 2007-09-14 | 2009-04-02 | Shiga Pref Gov | Biodegradable elastomer and method for producing the same |
| CN101503501A (en) * | 2009-03-02 | 2009-08-12 | 四川大学 | Biodegradable nontoxic amphipathic multi-block polyurethane material and preparation thereof |
| CN102585485A (en) * | 2012-01-06 | 2012-07-18 | 华南理工大学 | Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof |
| CN102911335A (en) * | 2012-10-19 | 2013-02-06 | 奥斯汀新材料（张家港）有限公司 | Preparation method of natural macromolecular modified thermoplastic polyurethane elastomer |
| CN103450649A (en) * | 2013-09-13 | 2013-12-18 | 四川大学 | High-toughness polylactic acid/crosslinked polyurethane compound and preparation method thereof |
| KR20140076033A (en) * | 2012-12-12 | 2014-06-20 | 주식회사 에스아이켐 | Manufacturing method of biodegradable biourethane resin containing vegetable polyol and poly(latic acid) |
-
2017
- 2017-06-30 CN CN201710519346.6A patent/CN107312322A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009067923A (en) * | 2007-09-14 | 2009-04-02 | Shiga Pref Gov | Biodegradable elastomer and method for producing the same |
| CN101503501A (en) * | 2009-03-02 | 2009-08-12 | 四川大学 | Biodegradable nontoxic amphipathic multi-block polyurethane material and preparation thereof |
| CN102585485A (en) * | 2012-01-06 | 2012-07-18 | 华南理工大学 | Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof |
| CN102911335A (en) * | 2012-10-19 | 2013-02-06 | 奥斯汀新材料（张家港）有限公司 | Preparation method of natural macromolecular modified thermoplastic polyurethane elastomer |
| KR20140076033A (en) * | 2012-12-12 | 2014-06-20 | 주식회사 에스아이켐 | Manufacturing method of biodegradable biourethane resin containing vegetable polyol and poly(latic acid) |
| CN103450649A (en) * | 2013-09-13 | 2013-12-18 | 四川大学 | High-toughness polylactic acid/crosslinked polyurethane compound and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610618A (en) * | 2018-04-17 | 2018-10-02 | 杨建军 | A kind of degradable plastic film and preparation method thereof |
| CN109694494A (en) * | 2018-12-21 | 2019-04-30 | 山东一诺威聚氨酯股份有限公司 | Biodegradable thermoplastic polyurethane elastomer expanded bead and preparation method thereof |
| WO2020125577A1 (en) * | 2018-12-21 | 2020-06-25 | 山东一诺威聚氨酯股份有限公司 | Biodegradable thermoplastic polyurethane elastomer foam beads and preparation method therefor |
| CN110790889A (en) * | 2019-11-20 | 2020-02-14 | 苏州市雄林新材料科技有限公司 | Polarity-controllable TPU film and preparation method thereof |
| CN110903452A (en) * | 2019-11-22 | 2020-03-24 | 广州睿特新材料科技有限公司 | Preparation method of lactic acid copolymer with high relative molecular mass |
| CN115260433A (en) * | 2022-06-24 | 2022-11-01 | 中国科学院宁波材料技术与工程研究所 | Bio-based high-damping thermoplastic polyurethane elastomer material and preparation method and application thereof |
| CN117510791A (en) * | 2023-12-29 | 2024-02-06 | 山东一诺威聚氨酯股份有限公司 | Biodegradable bio-based thermoplastic polyurethane elastomer and preparation method thereof |
| CN117510791B (en) * | 2023-12-29 | 2024-04-23 | 山东一诺威聚氨酯股份有限公司 | Biodegradable bio-based thermoplastic polyurethane elastomer and preparation method thereof |
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Application publication date: 20171103 |