CN108314769A - A kind of reactive extrursion prepares the method and its application of polylactic acid based polyurethanes elastomer - Google Patents
A kind of reactive extrursion prepares the method and its application of polylactic acid based polyurethanes elastomer Download PDFInfo
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- CN108314769A CN108314769A CN201710032508.3A CN201710032508A CN108314769A CN 108314769 A CN108314769 A CN 108314769A CN 201710032508 A CN201710032508 A CN 201710032508A CN 108314769 A CN108314769 A CN 108314769A
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- polylactic acid
- based polyurethanes
- acid based
- reactive extrursion
- polyurethanes elastomer
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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
- C08G18/28—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/0895—Manufacture of polymers by continuous processes
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
Abstract
The invention discloses the method and its application that a kind of reactive extrursion prepares polylactic acid based polyurethanes elastomer.The preparation method includes:Copolymer of poly lactic acid polyalcohol, isocyanate compound, small molecule polyol and catalyst are uniformly mixed in double screw extruder, and carry out reactive extrursion, obtains the polylactic acid based polyurethanes elastomer.The present invention preparation method is easy to operate, production efficiency is high, and it is raw materials used derive from a wealth of sources, be suitable for large-scale production.Moreover, the preparation method of the present invention can adjust reaction extrusion process at any time, it is suitable for different material systems, and can be used for producing different types of product.Meanwhile polylactic acid based polyurethanes elastomer prepared by the present invention is biodegradable, and there is excellent biocompatibility, it can be used for disposable medical instrument, and environmental pollution will not be caused.
Description
Technical field
Present invention relates particularly to the method and its application that a kind of reactive extrursion prepares polylactic acid based polyurethanes elastomer, belong to
Technical field of polymer preparation.
Background technology
Currently, the main material of the medical instruments such as disposable transfusion device is polyvinyl chloride (PVC).But due in medical PVC
Usually contain toxic plasticizer (such as phthalic acid two (2- ethyls) own ester, vehicle economy HP, and weight fraction is up to 40%-
60%), unpolymerized carcinogenic monomeric vinyl chloride (Vinyl chloride), and after adsorbing these materials, some drugs can drop
Low therapeutic effect, while this medical PVC itself does not have biodegradability, and safety environment is easily caused after use.
Therefore, Chinese food Drug Administration requires infusion apparatus manufacturing enterprise that should research and develop environmentally friendly, safe, disposable defeated without absorption
Liquid device replaces PVC.
Industry research staff succeeds in developing at present and commercialized substitution PVC material has:Thermoplastic elastomer (TPE) (TPE),
Thermoplastic polyurethane (TPU) with excellent biocompatibility.But all these materials all do not have biodegradability, make
With rear easy formation biological pollution and long-term environmental pollution.In addition, TPU is typically to be obtained by solution polymerization process, production
It is inefficient, and it be easy to cause environmental pollution.
Invention content
The main purpose of the present invention is to provide a kind of reactive extrursion prepare polylactic acid based polyurethanes elastomer method and
It is applied, to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
An embodiment of the present invention provides a kind of methods that reactive extrursion prepares polylactic acid based polyurethanes elastomer comprising:
In double screw extruder uniformly by copolymer of poly lactic acid polyalcohol, isocyanate compound, small molecule polyol and catalyst
Mixing, and reactive extrursion is carried out, obtain the polylactic acid based polyurethanes elastomer.
Among some preferred embodiments, the condition of the reactive extrursion includes:Extruder temperature is preferably 90~200
DEG C, screw speed is preferably 20~200 revs/min.
Among some preferred embodiments, the copolymer of poly lactic acid polyalcohol, isocyanate compound and small molecule
The molal weight of polyalcohol is than preferably 1:(2~6):(0.5~5);The dosage of the catalyst is that copolymer of poly lactic acid is polynary
0.1wt% of alcohol or so.
Among some more specific embodiment, the reactive extrursion prepares the side of polylactic acid based polyurethanes elastomer
Method specifically includes:Twin-screw is added in copolymer of poly lactic acid polyalcohol, isocyanate compound, small molecule polyol and catalyst
Reactive extrursion is carried out in extruder, later by making melt at fine strip shape, cooling, acquisition polylactic acid based polyurethanes bullet at a mouth mold
Property body.
Further, the material charging region temperature of the double screw extruder is preferably 90~120 DEG C, and reaction zone temperature is preferably
110~200 DEG C, extrusion zone temperature is preferably 110~160 DEG C.
The embodiment of the present invention additionally provides reactive extrursion above-mentioned and prepares the method for polylactic acid based polyurethanes elastomer in system
Application in standby disposable medical instrument.
Compared with prior art, advantages of the present invention includes:
1. the method for reactive extrursion preparation polylactic acid based polyurethanes elastomer provided by the invention is easy to operate, production efficiency
Height, and it is raw materials used derive from a wealth of sources, be suitable for large-scale production;
2. the method that reactive extrursion provided by the invention prepares polylactic acid based polyurethanes elastomer can adjust reaction at any time
Expressing technique is suitable for different material systems, for producing different types of product.
3. can be effectively improved as raw material using polylactic acid-polycaprolactone co-polymer polyalcohol in the method for the present invention
The hydrolytic resistance and toughness of pure polylactic acid polyurethane elastomer.
4. using polylactic acid based polyurethanes elastomer prepared by method provided by the invention biodegradable and with excellent
Biocompatibility, can be used for disposable medical instrument, and environmental pollution will not be caused.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
A kind of reactive extrursion that the one side of the embodiment of the present invention provides prepares the side of polylactic acid based polyurethanes elastomer
Method includes:By copolymer of poly lactic acid polyalcohol, isocyanate compound, small molecule polyol and catalyst in double screw extruder
In uniformly mix, carry out reactive extrursion, obtain the polylactic acid based polyurethanes elastomer.
Among some preferred embodiments, the condition of the reactive extrursion includes:Extruder temperature is preferably 90~200
DEG C, especially preferably 120~180 DEG C, screw speed is preferably 20~200 revs/min, especially preferably 30~100 revs/min.
Among some preferred embodiments, the copolymer of poly lactic acid polyalcohol, isocyanate compound and small molecule
The molal weight of polyalcohol is than preferably 1:(2~6):(0.5~5), especially preferably 1:(2.5~4):(1~3).
Among some preferred embodiments, the copolymer of poly lactic acid polyalcohol mainly by lactic acid and caprolactone polycondensation or
Lactide is prepared with caprolactone ring-opening copolymerization.
Preferably, the copolymer of poly lactic acid polyalcohol is polylactic acid-polycaprolactone co-polymer polyalcohol.
Preferably, the number-average molecular weight of the copolymer of poly lactic acid polyalcohol is between 500~4000.
Among some preferred embodiments, the isocyanate compound includes toluene di-isocyanate(TDI), diphenylmethyl
Any one in alkane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or two or more groups
It closes, but not limited to this.
Further, the small molecule polyol includes ethylene glycol, propylene glycol, butanediol, hexylene glycol, decanediol, 12
Any one in alkyl diol, hydroquinone two hydroxy ethyl ether, trimethylolpropane or two or more combinations, but be not limited to
This.
Further, the catalyst includes arbitrary in stannous octoate, triethylenediamine, dibutyl tin laurate
A combination of one or more, but not limited to this.
Wherein, any suitable amounts known to industry may be used in the catalyst, such as can be that the polylactic acid is total
The 0.1wt% or less (be preferably greater than 0 and be less than or equal to 0.1wt%) of polymers polyol quality, the addition of catalyst is not only
It can accelerate reaction speed, be conducive to reactive extrursion, but also the performance that can promote product to a certain extent (includes but not limited to
Its toughness, hydrolytic resistance etc.).
Among some more specific embodiment, the reactive extrursion prepares the side of polylactic acid based polyurethanes elastomer
Method specifically includes:Twin-screw is added in copolymer of poly lactic acid polyalcohol, isocyanate compound, small molecule polyol and catalyst
Reactive extrursion is carried out in extruder, later by making melt at fine strip shape, cooling, acquisition polylactic acid based polyurethanes bullet at a mouth mold
Property body.
In some preferred embodiment, the material charging region temperature of the double screw extruder is preferably 90~120 DEG C, especially excellent
100~110 DEG C are selected as, reaction zone temperature is preferably 110~200 DEG C, and extrusion zone temperature is preferably 110~160 DEG C.
The embodiment of the present invention additionally provides reactive extrursion above-mentioned and prepares the method for polylactic acid based polyurethanes elastomer in system
Application in standby disposable medical instrument.For example, the disposable medical infusion apparatus include disposable transfusion device, infusion bottle,
Infusion bag, blood transfusion apparatus or blood taking bag etc., and it is without being limited thereto.
Further, the embodiment of the present invention additionally provides a kind of device, and the polylactic acid base prepared it includes the above method is poly-
Urethane elastomer.In particular, the regional area of described device is deformable to be made of the polylactic acid based polyurethanes elastomer
Region, alternatively, at least one element in described device is the deformable member being made of the polylactic acid based polyurethanes elastomer
Part.
Wherein, the device includes disposable medical infusion apparatus, for example, disposable transfusion device, infusion bottle, infusion bag,
Blood transfusion apparatus, blood taking bag etc., and it is without being limited thereto.
Below by way of several embodiments technical solution that present invention be described in more detail.However, selected embodiment is only
For illustrating the present invention, and do not limit the scope of the invention.
Embodiment 1:Polylactic acid-polycaprolactone that 500g number-average molecular weights are 2000 is taken to be copolymerized dihydric alcohol, 22.5g 1,4-
Butanediol, 62.5g methyl diphenylene diisocyanates and the mixing of 0.01g dibutyl tin laurates, are injected double by metering pump
Screw extruder obtains polylactic acid based polyurethanes elastomer by reactive extrursion, cooling, and one of which typical case's polylactic acid base is poly-
The data of mechanical ginseng of urethane elastomer is shown in Table 1.
The parameter setting of double screw extruder is as follows in the present embodiment:
Embodiment 2:Take 500g number-average molecular weights be 1000 polylactic acid-polycaprolactone be copolymerized dihydric alcohol, 59g hexylene glycols,
125.1g methyl diphenylene diisocyanates and the mixing of 0.01g dibutyl tin laurates are injected twin-screw by metering pump and are squeezed
Go out machine, by reactive extrursion, cooling, obtains polylactic acid based polyurethanes elastomer, data of mechanical is referring to 1 institute of table
Show.
The parameter setting of double screw extruder is as follows in the present embodiment:
Embodiment 3:Polylactic acid-polycaprolactone that 500g number-average molecular weights are 2000 is taken to be copolymerized dihydric alcohol, the 43.6g last of the ten Heavenly stems two
Alcohol, 68g methyl diphenylene diisocyanates and the mixing of 0.01g stannous octoates, inject double screw extruder by metering pump, pass through
Reactive extrursion, cooling, obtain polylactic acid based polyurethanes elastomer, and data of mechanical ginseng is shown in Table 1.
The parameter setting of double screw extruder is as follows in the present embodiment:
Embodiment 4:Polylactic acid-polycaprolactone that 500g number-average molecular weights are 2000 is taken to be copolymerized dihydric alcohol, 50.6g dodecanes
Base glycol, 65g methyl diphenylene diisocyanates and the mixing of 0.01g triethylenediamines are injected twin-screw by metering pump and are squeezed
Go out machine, by reactive extrursion, cooling, obtains polylactic acid based polyurethanes elastomer, data of mechanical is referring to 1 institute of table
Show.
The parameter setting of double screw extruder is as follows in the present embodiment:
The data of mechanical (100mm/min) of each product in 1 embodiment 1-4 of table
Tensile strength (MPa) | Elongation at break (%) | Hydrolytic resistance | |
Embodiment 1 | 25.1 | 340 | One week |
Embodiment 2 | 22.5 | 300 | One week |
Embodiment 3 | 15.0 | 650 | One week |
Embodiment 4 | 17.6 | 560 | One week |
Comparative example 1 | 35 | 210 | Four days |
Comparative example 1:Take the polylactic acid dihydric alcohol, 22.5g 1,4- butanediols, 62.5g bis- that 500g number-average molecular weights are 2000
Methylenebis phenyl isocyanate and the mixing of 0.01g dibutyl tin laurates, inject double screw extruder by metering pump, pass through
Reactive extrursion, cooling obtain polylactic acid polyurethane elastomer, the mechanical property of one of which typical case's polylactic acid based polyurethanes elastomer
Energy test data ginseng is shown in Table 1.
The parameter setting of double screw extruder is as follows in this comparative example:
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from the concept of the present invention, other modification and improvement can also be made, these are all
It belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of method that reactive extrursion prepares polylactic acid based polyurethanes elastomer, it is characterised in that including:Polylactic acid is copolymerized
Object polyalcohol, isocyanate compound, small molecule polyol and catalyst uniformly mix in double screw extruder, and carry out anti-
It should squeeze out, obtain the polylactic acid based polyurethanes elastomer.
2. the method that reactive extrursion according to claim 1 prepares polylactic acid based polyurethanes elastomer, which is characterized in that institute
The condition for stating reactive extrursion includes:Extruder temperature is 90~200 DEG C, and screw speed is 20~200 revs/min.
3. the method that reactive extrursion according to claim 2 prepares polylactic acid based polyurethanes elastomer, which is characterized in that institute
The condition for stating reactive extrursion includes:The material charging region temperature of the double screw extruder is 90~120 DEG C, reaction zone temperature 110
~200 DEG C, extrusion zone temperature is 110~160 DEG C.
4. the method that reactive extrursion according to claim 2 prepares polylactic acid based polyurethanes elastomer, it is characterised in that packet
It includes:Copolymer of poly lactic acid polyalcohol, isocyanate compound, small molecule polyol and catalyst are added twin-screw extrude
Reactive extrursion is carried out, later by making melt at fine strip shape, cooling, acquisition polylactic acid based polyurethanes elastomer at a mouth mold.
5. the method that reactive extrursion according to claim 1 prepares polylactic acid based polyurethanes elastomer, it is characterised in that:Institute
The molar ratio for stating copolymer of poly lactic acid polyalcohol, isocyanate compound and small molecule polyol is 1:(2~6):(0.5~5),
Preferably, the dosage of the catalyst is the 0.1wt% or less of copolymer of poly lactic acid polyalcohol.
6. the method that reactive extrursion prepares polylactic acid based polyurethanes elastomer according to claim 1 or 5, feature exist
In:The copolymer of poly lactic acid polyalcohol is mainly prepared by lactic acid and caprolactone polycondensation or lactide with caprolactone ring-opening copolymerization
It forms;Preferably, the copolymer of poly lactic acid polyalcohol is polylactic acid-polycaprolactone co-polymer polyalcohol;Preferably, described poly-
The number-average molecular weight of lactic acid copolymer polyalcohol is 500~4000.
7. the method that reactive extrursion prepares polylactic acid based polyurethanes elastomer according to claim 1 or 5, feature exist
In:The isocyanate compound includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate
Any one in ester, hexamethylene diisocyanate or two or more combinations.
8. the method that reactive extrursion prepares polylactic acid based polyurethanes elastomer according to claim 1 or 5, feature exist
In:The small molecule polyol include ethylene glycol, propylene glycol, butanediol, hexylene glycol, decanediol, dodecanediol, to benzene two
Any one in phenol dihydroxyethyl ether, trimethylolpropane or two or more combinations.
9. the method that reactive extrursion prepares polylactic acid based polyurethanes elastomer according to claim 1 or 5, feature exist
In:The catalyst include in stannous octoate, triethylenediamine, dibutyl tin laurate any one or it is two or more
Combination.
10. reactive extrursion as claimed in any one of claims 1-9 wherein prepares the method for polylactic acid based polyurethanes elastomer in system
Application in standby disposable medical instrument.
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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 |
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