CN104130367A - Polymerization method of biodegradable high-barrier thermoplastic polymer - Google Patents
Polymerization method of biodegradable high-barrier thermoplastic polymer Download PDFInfo
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- CN104130367A CN104130367A CN201410325252.1A CN201410325252A CN104130367A CN 104130367 A CN104130367 A CN 104130367A CN 201410325252 A CN201410325252 A CN 201410325252A CN 104130367 A CN104130367 A CN 104130367A
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Abstract
The invention provides a polymerization method of a biodegradable high-barrier thermoplastic polymer. Polymer monomers comprising (a) composite polyatomic alcohol of polycarbonate segment and polyether segment; (b) one or more small-molecular compounds with two or more hydroxyl groups and amino groups; (c) one or more diisocyanate compounds; and (d) one or more cross-linking agents. A preparation method comprises the steps that (a), (b) and (c) are subjected to mixed reaction; and the monomer (d) is added into the product of the mixed reaction, such that grafting cross-linking is carried out. According to the invention, polymerization monomers are finely selected, and reaction route and conditions are reasonably designed, such that the polymer has good barrier property against water vapour and oxygen, and that the polymer has good physical and mechanical performances. The polymer also has good biodegradability and wider application scope.
Description
Technical field
The present invention relates to a kind of polymkeric substance, particularly a kind of high molecular, biodegradable, the biodegradable high-barrier thermoplastic polymer polymerization process with higher steam, oxygen obstruction.
Background technology
The biodegradable material of artificial preparation is that people are a kind of novel high polymer material that reply commodity polymer material brings " white pollution " to develop, this type of material can adopt existing Process Technology of Polymer technology production articles for daily use, mainly disposable packaging, as bag film, cup, tableware, mulch film and other goods.The great convenience that biodegradable material brings to daily life, has alleviated white pollution.Be subject to the restriction of material property and processing technology, the Application Areas of biodegradable material is only confined on the disposable packaging in short life cycle at present.Recent study mechanism and enterprise are turning to sight the functionalization field of biodegradable material, wish that biodegradable material has the high molecular performance of engineering, but have after application function is lost, want to degrade immediately, the application of these through engineering approaches is as weather resistance automobile component, household electrical appliance component, extra package require as the Freshkeeping Packaging such as water vapor rejection, oxygen obstruction, along with the development of technology, the expansion of biodegradable material frontier more and more comes into one's own, and also wishes to obtain good economic benefit.
We know, CO
2when thering is biodegradability with the pure diadactic structure high-molecular biologic degradable material of epoxy compounds polymerization, show good steam, the barrier of oxygen, but residual due to a large amount of catalyzer in physicals poor (as poor tensile strength, low temperature brittleness) and production process, the application of such biodegradable material is restricted, thereby never has heavy industrialization.
The present invention is directed to above defect, look for another way, first selected CO
2a) monomer of dibasic alcohol with the synthetic low-molecular-weight composite structure that contains active function groups of epoxy compounds, and Removal of catalyst, adopt the mode of production of polyurethane thermoplastic, the ratio of selected each monomer, Optimizing Technical, production one had both had biodegradability, kept again good steam, the type material of oxygen-barrier property, and this kind of material overcome the CO of pure diadactic structure
2the shortcoming poor with low temperature brittleness, the physical and mechanical properties of epoxy compounds polymkeric substance, is used the film of this kind of materials processing to have good tear strength and snappiness, is CO
2a new industrialized route has been opened up in based polyalcohol application.
As Chinese patent 201110355699 discloses a kind of taking poly (propylene carbonate) as the soft section of method of preparing Polyurethane Thermoplastic Elastomer, first to add poly (propylene carbonate) polyvalent alcohol to react vulcabond, catalyzer, after reaction, add chainextender to carry out chain extending reaction, dry solidification obtains Polyurethane Thermoplastic Elastomer again.This invention is not carried out qualitative and selected to the structure of poly (propylene carbonate), thus can not keep the barrier property of material to steam, oxygen and meet biodegradable requirement, and products therefrom poor tensile strength and low temperature brittleness are not also improved.
Summary of the invention
The term " biodegradable " the present invention relates to refers under the effect of microorganism and enzyme, and organic compound is decomposed into carbonic acid gas and water or methane by microorganism and enzyme, and the mineralising salt of contained material and new biomass.
In order to overcome the deficiencies in the prior art, the invention provides the biodegradable high-barrier thermoplastic polymer of a kind of high molecular method.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of biodegradable obstruct thermoplastic polymer, is formed by following monomer polymerization:
A) Pluronic polyols, contains polycarbonate segment and polyether segment structure in its structure, its molecular structural formula is:
Wherein: R '=H or/CH
3one, f=2 or 3, x>=1, y>=1;
B) one or more micromolecular compounds with two or more hydroxyls, amido;
C) one or more diisocyanate compounds;
D) one or more linking agents.
Described monomer a) the polycarbonate segment in Pluronic polyols is one or more mixed structure of poly (propylene carbonate) structure, polymerized thylene carbonate ethyl ester; Described polyether segment is one or both mixed structure of polyoxyethylene, polyoxytrimethylene; Described polycarbonate segment is all generated together with in synthesis of epoxy compounds process by carbonic acid gas with polyether segment; Described monomer is shared molar percentage >=50% of polycarbonate segment in Pluronic polyols a); The described monomer a) molecular-weight average of Pluronic polyols is between 500～10000.
Described monomer b) is selected from small molecules glycol, preferably from C
2~ C
30straight or branched aliphatic dihydroxy alcohol, more preferably from C
2~ C
10straight chain or side chain aliphatic dihydroxy alcohol, for example: ethylene glycol, 1,2-PD, 1,3-PD, BDO, a kind of in 1,2-butyleneglycol, hexylene glycol or more than one.Or monomer b) is selected from small molecules diamine based compound, as: chloro-4, the 4 ' diaminodiphenylmethane of quadrol, 3,3 '-bis-, diethyl toluene diamine.Or monomer b) is selected from the glycol containing naphthalene structure, for example two naphthyl ethylene glycol, naphthyl ethylene glycol.
Described monomer is c) vulcabond, vulcabond is preferably from tolylene diisocyanate, hexamethylene diisocyanate, 2,4 ' '-diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, more preferably one or more of tolylene diisocyanate, hexamethylene diisocyanate and 4,4 ' '-diphenylmethane diisocyanate.
Described monomer d) is selected from organo-peroxide class and causes linking agent, preferably from ditertiary butyl peroxide, two t-amyl peroxy things, 2, 2-di-t-butyl peroxy butane, 2, 5 dimethylhexane-2, 5 ditertiary butyl peroxides, 2, 5 dimethyl-3-hexin-2, 5-ditertiary butyl peroxide, dicumyl peroxide, two (2-tert-butyl hydroperoxide sec.-propyl) benzene, t-butylperoxy isopropyl benzene, tert-butyl hydroperoxide-2-ethylhexyl carbonic ether, peroxycarbonates, more preferably from 2, 5 dimethylhexane-2, 5 ditertiary butyl peroxides, dicumyl peroxide, tert-butyl hydroperoxide-2-ethylhexyl carbonic ether, one or more of peroxycarbonates.
Described monomer is a): b): c): mole ratio be 1:(1-4): (2-5).
Described monomer weight part d) be monomer a), b), c) gross weight 0.01%～5%, be particularly preferably 0.01%～1%.
A preparation method for biodegradable high-barrier thermoplastic polymer, comprises the steps:
(1) polymerization single polymerization monomer a) is heated and vacuumizes and remove moisture
(2) by step (1) product and b), c) hybrid reaction;
(3) in the mixed reactant of step (2) gained, add monomer d) again, carry out graft crosslinking.
Above-mentioned steps (1) temperature is 80-100 DEG C, and the time is 0.5-10 hour, vacuumizes 90-100Pa; The reaction of described step (2) is to carry out under the existence of catalyzer, and temperature of reaction is 60 DEG C-200 DEG C, and the reaction times is 1-15 minute, reacts by twin-screw extrusion.
The molecular structure that step (2) forms be step (1) polycondensation product and a), b), c) the unordered paradigmatic structure of monomer, and keep the weight content of phenyl compound to be less than 20%.
For ensureing the smooth enforcement of step (2), after raw material used step (2) need being mixed under high speed more than 6000r/min, inject twin screw extruder.
Above-mentioned steps (3) utilizes liquid or powder automatic gauge feeding device to add in twin screw extruder stage casing.
Above-mentioned steps (2) adopts environment-friendly type catalyzer, not stanniferous, plumbous, cadmium, chromium, zinc class heavy metal ion.
The present invention also provides a kind of biodegradable obstruct thermoplastic polymer to prepare the application of the aspects such as layered product, hot melt adhesive, foaming product, paper coating, film, sheet material, raw material blend.Described biodegradable obstruct thermoplastic polymer can use separately, also can use with other material composite, and " other material " described here comprising: 1) other biodegradable material; 2) inorganic filler; 3) organic weighting material, as: starch, Mierocrystalline cellulose, xylogen etc.; 4) all kinds of processing aids; 5) all kinds of barrier materials, as: ethylene/vinyl alcohol copolymer, vinylidene chloride copolymer, the fine multipolymer of propylene, nylon, polyethyleneterephthalate etc.; 6) other commodity polymer material, as polypropylene, polyethylene.
The preparation of a kind of biodegradable obstruct thermoplastic polymer provided by the invention and purposes, provide a kind of can mass-producing, the functional living being degradable material of industrialization, functionalization is exactly the barrier to steam, oxygen,
Concrete beneficial effect is as follows:
(1) the selected synthon of the present invention, appropriate design reaction scheme and condition, make in molecular structure, there is a large amount of Sauerstoffatoms, thereby make molecular chain show higher polarity, make polymer in the time contacting with oxygen with steam, form a large amount of hydrogen bonds, stop steam and the motion of oxygen in macromolecular material, polymkeric substance is had steam, oxygen has good barrier, in molecular structure, carbonic acid ester bond has the ratio that reaches biological degradation requirement simultaneously, these structures provide polymkeric substance good physical and mechanical properties simultaneously, make this kind of polymkeric substance become independent use or a kind of material with the common use of other material, in building-up process, adopt novel environment friendly catalyzer, avoided the pollution to environment, make it have Application Areas widely.
(2) the present invention adopts high-intensity mixing, reaction process, make reaction monomers polymerization more even, independently polycondensation separately, crosslinked, graft reaction are controlled effectively, guarantee to form crosslinked, cladodification structure in polymkeric substance, eliminate owing to mixing the inhomogeneous brilliant point defect of bringing, given tensile strength, elongation at break, notched Izod impact strength and obstruct homogeneity that polymkeric substance is higher.
In sum, the present invention is by raw-material preferred and process reform, and the polymkeric substance of gained has good biodegradability, under aerobic composting conditions, in 90 days, degrades more than 60%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Further prove and describe technical scheme of the present invention, it is pointed out that above-described embodiment is only in order to understand better the present invention, and not as limitation of the present invention.
Wherein water vapor transmittance adopts infrared checking method, establishing criteria: ASTM F1249-2001, and test set: Mocon moisture-inhibiting tester, test condition: 23 DEG C, 82%RH; OTR oxygen transmission rate adopts isopiestic method, establishing criteria: ASTM D3985-1995 " by a coulomb test method for sensor test film oxygen transit dose ", and test set: Mocon oxygen flow tester, test condition: 23 DEG C, 0%RH.Biological degradation experimental basis standard GB/T20197-2006, experimental technique is according to GB/T19277-2003 standard.
Melt flow rate (MFR) testing method is according to GB/T3682-2000 standard, and probe temperature is 190 DEG C, loads as 2.16kg.
Physical and mechanical properties establishing criteria: GB/T1040-2006 plastic tensile performance test standard
Embodiment 1
Get poly (propylene carbonate) ester structure and account for molar percentage 55%, the Pluronic polyols 250kg that accounts for 45% molar percentage of polyoxytrimethylene ether structure, molecular weight is 2500, pour in reactor, add 1, 4 butyleneglycol 18g, intensification is stirred to 90 DEG C, and vacuumize 1-3 hour, vacuum tightness 100pa, after stopping vacuumizing, add environment-friendly type catalysts, stir, by 80kg 4, 4 ' '-diphenylmethane diisocyanate fusing (MDI), then the polyvalent alcohol mixing and '-diphenylmethane diisocyanate by high-speed stirring in proportion, inject twin screw extruder, reaction is extruded, automatically add 0.05% dicumyl peroxide with electronic weighing balance at twin screw interlude, obtain transparent polymer 01, test melt flow rate (MFR) MFR=2.3g/10min
Embodiment 2
Get the sub-propyl ester structure of polycarbonate and account for molar percentage 70%, polyoxytrimethylene ether structure accounts for the Pluronic polyols 200g of 30% molar percentage, molecular weight is 2000, hydroxyl value 55mg(KOH)/g, add ethylene glycol 18.6g, intensification is stirred to 90 DEG C, and vacuumize 1-3 hour, vacuum tightness 100pa, after stopping vacuumizing, add environment-friendly type catalysts, stir, by 110g 4, 70 DEG C of fusings of 4 ' '-diphenylmethane diisocyanate, then the polyvalent alcohol mixing and '-diphenylmethane diisocyanate, high-speed stirring in proportion, inject twin screw extruder, reaction is extruded, automatically add 0.05% dicumyl peroxide with electronic weighing balance at twin screw interlude, obtain transparent polymer 02, test melt flow rate (MFR) MFR=1.5g/10min
Embodiment 3
Get poly (propylene carbonate) ester structure molar percentage than the compound polyvalent alcohol 250kg that accounts for 55%, polyoxytrimethylene ether structure accounts for 45% molar percentage, molecular weight is 2500, add quadrol 12kg, intensification is stirred to 90 DEG C, and vacuumizing 1-3 hour, vacuum tightness 90pa, after stopping vacuumizing, add environment-friendly type catalysts, stir; By 80kg 4,70 DEG C of fusings of 4 ' '-diphenylmethane diisocyanate, then the polyvalent alcohol mixing and 4,4 ' '-diphenylmethane diisocyanate, high-speed stirring in proportion, inject twin screw extruder reaction and extrudes, automatically add 0.065% two-(t-butyl peroxy sec.-propyl) benzene to obtain translucent polymer 03, test melt flow rate (MFR) MFR=2.0g/10min at twin screw interlude with electronic weighing balance
Embodiment 4
Choose Pluronic polyols 500 kg that polymerized thylene carbonate ethyl ester structure accounts for molar percentage 60%, polyoxyethylene ether structure and account for 40% molar percentage, molecular weight 4985,, pour in reactor, add quadrol 18kg, intensification is stirred to 90 DEG C, and vacuumizing 1-3 hour, vacuum tightness 110pa, after stopping vacuumizing, add environment-friendly type catalyzer, stir; 67.3 kg hexamethylene diisocyanates are heated to 50 DEG C, by above-mentioned ready raw material high-speed stirring in proportion, inject twin screw extruder, automatically add in proportion 0.5% 2-(t-butyl peroxy sec.-propyl) at twin screw interlude, all obtain translucent polymkeric substance 04, test melt flow rate (MFR) MFR=4.3g/10min
Embodiment 5
Choose that polymerized thylene carbonate ethyl ester structure accounts for molar percentage 63%, polyoxyethylene ether structure molar percentage accounts for 37% Pluronic polyols 300kg, molecular weight is 3000, and hydroxyl value is 38, pours in reactor, and add and add 1,4 butyleneglycol 27 kg, heat up and are stirred to 90 DEG C, and vacuumize 1-3 hour, vacuum tightness 100pa, after stopping vacuumizing, add environment-friendly type catalyzer, stir; By 105 kg4,4 ' '-diphenylmethane diisocyanate is heated to 80 DEG C, by above-mentioned ready raw material high-speed stirring in proportion, inject twin screw extruder, automatically add in proportion 0.5%2,5 dimethylhexane-2,5 ditertiary butyl peroxides at twin screw interlude, all obtain translucent polymkeric substance 05, test melt flow rate (MFR) MFR=6.4g/10min.
The tensile property of the high molecular polymer of above-described embodiment resulting polymers 01-05 is tested with reference to GB/T17037.1-1997 preparation standard shape dumbbell shape, the long 146mm of size, thickness 4mm, two ends width 20mm, intermediate width 10mm, tensile property is tested according to GB/T1040-2006 standard testing, draw speed 50mm/min, middle gauge length 50mm, tests respectively above sample, and record data.
Notched Izod impact strength reference standard GB/T1843-2008 test
After polymkeric substance 1,2,3,4 is dried respectively, be blow molded into the film of 30um on inflation film manufacturing machine, blown film temperature is controlled between 140 DEG C-180 DEG C, places after one week, adopts described method test steam and oxygen-barrier property.
Relevant test data is as follows:
Polymkeric substance, under controlled composting condition, is determined its final aerobic biodegradability ability by the amount of carbon dioxide of measuring polymer biological degraded discharge.Polymer sample is mixed with compost, pours static compost container into, compost container is placed in the experimental situation of 58 ± 2 DEG C, uses through the air of supersaturation, carbon dioxide removal and carries out aeration.Aeration is imported to NaOH absorption unit, after absorbing with NaOH solution, the inorganic carbon that periodic measurement dissolves, the amount of carbon dioxide of emitting as accumulative total.
Compost container shakes weekly once, with anti-compaction, ensures that microorganism fully contacts with sample.
Sample polymer biological decomposition rate is as follows:
。
Claims (8)
1. a biodegradable obstruct thermoplastic polymer polymerization process, is characterized in that: described polymkeric substance is formed by following monomer polymerization:
A) Pluronic polyols, contains polycarbonate segment and polyether segment in its structure, its molecular structural formula is:
Wherein: R '=H or CH
3, f=2 or 3, x>=1, y>=1;
B) one or more micromolecular compounds with two or more hydroxyls and amido;
C) one or more diisocyanate compounds;
D) one or more linking agents;
Its preparation process is:
(1) by polymerization single polymerization monomer a), b) Hybrid Heating vacuumize and remove moisture;
(2) by step (1) product and c) hybrid reaction;
(3) in the mixed reactant of step (2) gained, add monomer d) again, carry out graft crosslinking;
Above-mentioned steps (1) temperature is 80-100 DEG C, and the time is 0.5-10 hour, vacuumizes 90-100Pa; The reaction of described step (2) is to carry out under the existence of catalyzer, and temperature of reaction is 60 DEG C-200 DEG C, and the reaction times is 1-15 minute, reacts by twin-screw extrusion;
The molecular structure that step (2) forms be step (1) polycondensation product and a), b), c) the unordered paradigmatic structure of monomer, and keep the weight content of phenyl compound to be less than 20%;
After mixing under high speed more than 6000r/min, step (2) raw material used injects twin screw extruder;
Step (3) utilizes liquid or powder automatic gauge feeding device to add in twin screw extruder stage casing;
Step (2) adopts environment-friendly type catalyzer, not stanniferous, plumbous, cadmium, chromium, zinc class heavy metal ion.
2. the biodegradable obstruct thermoplastic polymer of one according to claim 1 polymerization process, is characterized in that: described monomer a) the polycarbonate segment in Pluronic polyols is one or more mixed structure of poly (propylene carbonate) structure, polymerized thylene carbonate ethyl ester; Described polyether segment is one or both mixed structure of polyoxyethylene, polyoxytrimethylene; Described polycarbonate segment is all generated together with in synthesis of epoxy compounds process by carbonic acid gas with polyether segment; Described monomer is shared molar percentage >=50% of polycarbonate segment in Pluronic polyols a); The described monomer a) molecular-weight average of Pluronic polyols is between 500～10000.
3. a kind of biodegradable obstruct thermoplastic polymer polymerization process according to claim 1, is characterized in that: described monomer b) is selected from small molecules glycol, preferably from C
2~ C
30straight or branched aliphatic dihydroxy alcohol, more preferably from C
2~ C
10straight chain or side chain aliphatic dihydroxy alcohol, more preferably: ethylene glycol, 1,2-PD, 1,3-PD, BDO, a kind of in 1,2-butyleneglycol, hexylene glycol or more than one; Or monomer b) is selected from small molecules diamine based compound, preferably: one or more in chloro-4, the 4 ' diaminodiphenylmethane of quadrol, 3,3 '-bis-, diethyl toluene diamine; Or monomer b) is selected from the glycol containing naphthalene structure, preferably: two naphthyl ethylene glycol, naphthyl ethylene glycol a kind of or more than one.
4. according to the biodegradable obstruct thermoplastic polymer of the one polymerization process described in claims 1, it is characterized in that: described monomer is c) vulcabond, vulcabond is preferably from tolylene diisocyanate, hexamethylene diisocyanate, 2,4 ' '-diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, more preferably one or more of tolylene diisocyanate, hexamethylene diisocyanate and 4,4 ' '-diphenylmethane diisocyanate.
5. according to the biodegradable obstruct thermoplastic polymer of the one polymerization process described in claims 1, it is characterized in that: described monomer d) is selected from organo-peroxide class and causes linking agent, preferably from ditertiary butyl peroxide, two t-amyl peroxy things, 2, 2-di-t-butyl peroxy butane, 2, 5 dimethylhexane-2, 5 ditertiary butyl peroxides, 2, 5 dimethyl-3-hexin-2, 5-ditertiary butyl peroxide, dicumyl peroxide, two (2-tert-butyl hydroperoxide sec.-propyl) benzene, t-butylperoxy isopropyl benzene, tert-butyl hydroperoxide-2-ethylhexyl carbonic ether, peroxycarbonates, more preferably from 2, 5 dimethylhexane-2, 5 ditertiary butyl peroxides, dicumyl peroxide, tert-butyl hydroperoxide-2-ethylhexyl carbonic ether, one or more of peroxycarbonates.
6. the biodegradable obstruct thermoplastic polymer of one according to claim 1 polymerization process, is characterized in that: described monomer a): b): c): mole ratio be 1:(1-4): (2-5).
7. the biodegradable obstruct thermoplastic polymer of one according to claim 1 polymerization process, is characterized in that: described monomer weight part d) be monomer a), b), c) gross weight 0.01%～5%, be particularly preferably 0.01%～1%.
8. the polymerization process of a kind of biodegradable high-barrier thermoplastic polymer according to claim 1, it is characterized in that: the reaction of described step (2) is to carry out under the existence of catalyzer, the product of described step (2) hybrid reaction gained reacts by twin-screw extrusion.
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| CN201410325252.1A CN104130367A (en) | 2014-07-09 | 2014-07-09 | Polymerization method of biodegradable high-barrier thermoplastic polymer |
| PCT/CN2015/083567 WO2016004870A1 (en) | 2014-07-09 | 2015-07-08 | Polymerization method for biodegradable high-barrier thermoplastic polymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016004870A1 (en) * | 2014-07-09 | 2016-01-14 | 江苏中科金龙化工有限公司 | Polymerization method for biodegradable high-barrier thermoplastic polymer |
| WO2016004872A1 (en) * | 2014-07-09 | 2016-01-14 | 江苏中科金龙化工有限公司 | Biodegradable high-barrier thermoplastic polymer, preparation method therefor, and applications of polymer |
| CN110483728A (en) * | 2019-09-10 | 2019-11-22 | 青岛水性七彩新材料有限公司 | A kind of preparation method of strippable water-soluble polyurethane resin and the application in coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001208A (en) * | 1989-03-20 | 1991-03-19 | Reeves Brothers, Inc. | Linear polyurethane elastomer compositions based on mixed polycarbonate and polyether polyols |
| CN101535364A (en) * | 2006-11-15 | 2009-09-16 | 巴斯夫欧洲公司 | Process for producing flexible polyurethane foams |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0358555A3 (en) * | 1988-09-06 | 1991-05-08 | Daicel Chemical Industries, Ltd. | Polycarbonatediol composition and polyurethane resin |
| CN103030766B (en) * | 2013-01-04 | 2015-04-01 | 中国科学院长春应用化学研究所 | Carbon dioxide-based poly (carbonic ester-ether) polyurethane and preparation method thereof |
| CN104130367A (en) * | 2014-07-09 | 2014-11-05 | 江苏中科金龙化工有限公司 | Polymerization method of biodegradable high-barrier thermoplastic polymer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001208A (en) * | 1989-03-20 | 1991-03-19 | Reeves Brothers, Inc. | Linear polyurethane elastomer compositions based on mixed polycarbonate and polyether polyols |
| CN101535364A (en) * | 2006-11-15 | 2009-09-16 | 巴斯夫欧洲公司 | Process for producing flexible polyurethane foams |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016004870A1 (en) * | 2014-07-09 | 2016-01-14 | 江苏中科金龙化工有限公司 | Polymerization method for biodegradable high-barrier thermoplastic polymer |
| WO2016004872A1 (en) * | 2014-07-09 | 2016-01-14 | 江苏中科金龙化工有限公司 | Biodegradable high-barrier thermoplastic polymer, preparation method therefor, and applications of polymer |
| CN110483728A (en) * | 2019-09-10 | 2019-11-22 | 青岛水性七彩新材料有限公司 | A kind of preparation method of strippable water-soluble polyurethane resin and the application in coating |
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