CN103788313A - Lactic acid polymer and preparation method - Google Patents
Lactic acid polymer and preparation method Download PDFInfo
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- CN103788313A CN103788313A CN201210424998.9A CN201210424998A CN103788313A CN 103788313 A CN103788313 A CN 103788313A CN 201210424998 A CN201210424998 A CN 201210424998A CN 103788313 A CN103788313 A CN 103788313A
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Abstract
The invention discloses a lactic acid polymer and a preparation method. The preparation method comprises the following steps: 1)under the ring-opening polymerisation condition and existence of inert gas, a monomer a containing lactide is contacted with a ring-opening polymerisation catalyst and a ring-opening polymerisation initiator to obtain a lactide polymer, wherein the ring-opening polymerisation initiator is nonsaturated monohydric alcohol containing one double bond or epoxy compound containing double bonds; and 2)under free radical polymerization condition, the lactide polymer obtained in the step 1), a free radical polymerization initiator and a monomer are contacted for reacting to obtain the lactic acid polymer, wherein the monomer is the free radical polymerization monomer. The molecular weight of the lactic acid polymer is high.
Description
Technical field
The present invention relates to a kind of lactic acid polymer and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) is a kind of Biodegradable material, and its material acid can be made by W-Gum etc., becomes carbonic acid gas and water after decomposition, meets the requirement of environmental protection low-carbon (LC), therefore obtains the extensive attention of industry and deep research.Poly(lactic acid) second-order transition temperature is about 60 ℃ of left and right, and fusing point is 170 ℃ of left and right, performance can with PET, the materials such as PS are compared, can be for extruding, injection, blow molding, also can with other materials blend or copolymerization.The goods that obtain take poly(lactic acid) as raw material, have good biocompatibility and Bioabsorbable, and good biological degradability, and PLA has best heat impedance in biodegradable thermoplastic polymer material.Therefore,, as Biodegradable material, poly(lactic acid) has a good application prospect.
Conventional poly(lactic acid) has two kinds of synthetic methods, i.e. the ring-opening polymerization of rac-Lactide (cyclic dimer of lactic acid) and the direct polymerization of lactic acid.
Acid through direct polycondensation by lactic is directly to carry out polymerization by the lactic acid of refining, and is to be also the simplest method the earliest.This method production technique is simple, but the polymericular weight obtaining is low, and molecular weight distribution is wider, and its processing characteristics etc. still can not meet the needs of fibre-forming polymer; And acid through direct polycondensation by lactic reaction carries out under the condition higher than 180 ℃, the polymer pole obtaining is oxidizable painted, and application is subject to certain restrictions.
Rac-Lactide ring-opening polymerization production method can production high molecular poly(lactic acid), common preparation method comprises: first acid by dehydrating lactic cyclisation is made to rac-Lactide; Again rac-Lactide ring-opening polymerization is made to poly(lactic acid).Wherein the cyclisation of lactic acid and purification are difficult point and the keys of preparing rac-Lactide, and this method can make the poly(lactic acid) of high molecular, also meets preferably the requirement of fibre-forming polymer and bone immobilizing material etc.Rac-Lactide ring-opening polymerization is take Naturework company as representative, poly-lactic acid material that can production high molecular.But the poly(lactic acid) that the method prepares is linear structure, well-known, linear poly(lactic acid) can not form effective chain entanglement.In addition, linear PLA polymkeric substance because intensity is not good, the reason such as the low and poor processability of poor heat resistance, the 70 ℃ of left and right sudden change, material deliquescing, the fusing point intensity that just produce performance can not substitute traditional plastics requirement completely.The critical entanglement molecular weight of bibliographical information poly(lactic acid) is 16000.Therefore the branched chain molecule amount of synthetic polymer at least will exceed 20000 and could effectively improve processing characteristics.
Summary of the invention
The object of the invention is in order to overcome prior art neutral line lactic acid polymer molecular weight on the low sidely, the shortcoming that processing characteristics is poor, provides a kind of lactic acid polymer and preparation method thereof.
The preparation method who the invention provides a kind of lactic acid polymer, the method comprises the following steps:
(1) under ring-opening polymerization condition, under rare gas element exists, monomer component containing rac-Lactide is contacted with ring-opening polymerization initiator with ring-opening polymerization catalyst, obtain lactide polymer, wherein, described ring-opening polymerization initiator is the unsaturated monohydroxy-alcohol that contains two keys and/or the epoxy compounds that contains two keys;
(2), under radical polymerization condition, the lactide polymer that step (1) is obtained and radical polymerization initiator contact reacts, obtain lactic acid polymer.
The lactic acid polymer that the present invention also provides a kind of aforesaid method to prepare.
The present inventor finds, the preparation method of lactic acid polymer provided by the invention first carries out ring-opening polymerization polymer by rac-Lactide, under the existence of ring opening catalyst, caused the ring-opening polymerization polymer of rac-Lactide by unsaturated monohydroxy-alcohol and/or double bond containing epoxy compounds ring-opening polymerization, obtaining end group is on the lactide polymer of two keys, on this basis, add radical polymerization initiator to cause radical polymerization, , dexterously ring-opening polymerization and Raolical polymerizable are combined, complete the modification to described lactide polymer, because the lactic acid polymer that adopts method of the present invention to obtain has multiple side chains, the lactic acid polymer molecular chain obtaining increases, molecular weight is large.Meanwhile, because the two keys of end group in the micronucleus of lactide polymer formation are after crosslinked, more stable, in post-treatment, be difficult for occurring the change of molecular weight.And the method and other chain extension methods, compare and be more prone to control as methods such as isocyanic ester.
Embodiment
According to the preparation method of branching lactic acid polymer of the present invention, the method comprises the following steps:
((1) is under ring-opening polymerization condition, under rare gas element exists, monomer component containing rac-Lactide is contacted with ring-opening polymerization initiator with ring-opening polymerization catalyst, obtain lactide polymer, wherein, described ring-opening polymerization initiator is the unsaturated monohydroxy-alcohol that contains two keys and/or the epoxy compounds that contains two keys;
(2) under radical polymerization condition, step (1) is obtained to lactide polymer and radical polymerization initiator contact reacts, obtain lactic acid polymer.
According to the present invention, in order to obtain the lactic acid polymer with good processing characteristics, be mainly that the molecular weight of realizing lactic acid polymer by carry out branched modification on the basis of lactide polymer increases.Owing to needing only on the basis of rac-Lactide, introduce double bond containing end group by the ring-opening polymerization at rac-Lactide at lactide polymer, carry out again on this basis radical polymerization and will realize goal of the invention, therefore, the condition of divided ring polymerization of the present invention does not have special requirement, preferably, described ring-opening polymerization condition comprises that temperature is that 130-220 ℃, pressure are that 0-0.4MPa, time are 0.5-12 hour; Preferably, described temperature is that 170-200 ℃, pressure are that 0.07-0.1MPa, time are 0.5-4 hour.
According to the present invention, although the weight ratio of divided ring polymerization starter of the present invention, ring-opening polymerization catalyst and rac-Lactide does not have special requirement, in the preferred case, for the lactic acid polymer that makes to obtain has further improved processing characteristics, the weight ratio of described ring-opening polymerization initiator, ring-opening polymerization catalyst and rac-Lactide can be 1:0.05-1:200-1500, is preferably 1:0.1-0.8:400-1000.
According to the present invention, described rare gas element can be nitrogen and conventional rare gas element.
According to the present invention, described unsaturated monohydroxy-alcohol can various routines the unsaturated monohydroxy-alcohol as ring-opening polymerization initiator, two keys are wherein inertia under ring-opening polymerization condition, under preferable case, described ring-opening polymerization initiator is that carbonatoms is the unsaturated alcohol of 3-10, more preferably one or more in vinyl carbinol, 1-butylene alcohol and 2-butylene alcohol.
According to the present invention, described double bond containing epoxy compounds can various routines can participate in ring-opening polymerization or the double bond containing epoxy compounds with hydroxyl reaction, two keys are wherein inertia under ring-opening polymerization condition, under preferable case, described ring-opening polymerization initiator is that carbonatoms is the double bond containing epoxy compounds of 3-10, more preferably glytidyl methacrylate and/or 1,2-epoxy-5-hexene.
Described have ring-opening polymerization catalyst can for various routines as the catalyzer of ring-opening polymerization, under preferable case, described ring-opening polymerization catalyst is selected from one or more in stannous octoate, Dibutyltin oxide, titanic acid ester and aluminum isopropylate, more preferably stannous octoate.
According to the present invention, in a kind of embodiment, the method is also included in step (2), adds free yl polymerizating monomer.Although the present invention does not have special requirement to the weight ratio of lactide polymer, radical polymerization initiator and free yl polymerizating monomer, in the preferred case, for the lactic acid polymer that makes to obtain has further improved processing characteristics, the weight ratio of described lactide polymer, radical polymerization initiator and monomer can be 1000:0.05-5:1-50, is preferably 1000:0.1-1:1-30.
According to the present invention, in order to obtain the lactic acid polymer with good processing characteristics, be mainly that the molecular weight of realizing lactic acid polymer by carrying out branched modification on the basis of lactide polymer increases.Owing to needing only on the basis of lactide polymer, by introduce double bond containing end group when the rac-Lactide ring-opening polymerization in lactide polymer, cause again on this basis radical polymerization and will realize goal of the invention, therefore, the present invention does not have special requirement to the condition of radical polymerization, the condition of radical polymerization can suitably be adjusted according to the monomeric species that carries out radical polymerization, preferably, described radical polymerization condition comprises: institute's reaction conditions comprises that temperature is that 150-220 ℃, pressure are that 0-0.4MPa, time are 15-180 minute; Preferably, described temperature is that 170-200 ℃, pressure are that 0.1-0.2MPa, time are 30-90 minute.
According to the present invention, although the kind of free yl polymerizating monomer of the present invention does not have special requirement, the various monomers that radical polymerization can occur all can be realized the object of the invention, preferably, described free yl polymerizating monomer is selected from one or more in acrylic ester monomer, styrene monomer, unsaturated fatty acids monomer, polyhutadiene and polyisoprene, more preferably one or more in hydroxy-terminated polybutadienes, vinylbenzene, methyl methacrylate and methacrylic acid stearyl.
Described acrylic ester monomer has the structure shown in formula (I):
Formula (I),
Wherein, R
1and R
2independent is separately H or C
1-C
6alkyl.Described C
1-C
6the example of alkyl can include but not limited to: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, hexyl or isohexyl.Particularly, described acrylic ester monomer can be selected from one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, ethylacrylic acid methyl esters, ethyl propylene acetoacetic ester, ethyl propylene propyl propionate and ethyl propylene acid butyl ester.
Described styrene monomer has the structure shown in formula (II):
In formula (II), R
3can be C
6-C
20replacement or unsubstituted aryl, be preferably phenyl and by one or more C
1-C
5alkyl replace phenyl.
The present invention is not particularly limited for the kind of described radical polymerization initiator, can be the selection of this area routine.For example, described radical initiator can be peroxide radical initiator.Particularly, described peroxide initiator can be peroxidation (2-ethyl acid) tert-butyl ester, isopropyl benzene hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, peroxidized t-butyl perbenzoate and 2, one or more in 2-bis-(t-butyl peroxy) butane, be preferably peroxidation (2-ethyl acid) tert-butyl ester and/or 2,2-bis-(t-butyl peroxy) butane.
According to the present invention, as required, in the time of ring-opening polymerization, also contain alternatively monomer c containing in the monomer component of rac-Lactide, described monomer c is selected from least one in glycollide, caprolactone, butyrolactone, PDO, ring-type mutual-phenenyl two acid bromide two alcohol ester's oligopolymer and cyclic carbonate.
According to the present invention, although the present invention does not have special requirement to the weight ratio of monomer c and rac-Lactide, in the preferred case, for the lactic acid polymer that makes to obtain has further improved processing characteristics, the mol ratio of described monomer c and rac-Lactide can be 1:0.01-100.
According to the present invention, the present invention is also included in radical polymerization and finishes, and adopts the method vacuumizing to remove unreacted monomer and the low molecule by product that reacts generation in reaction system.The ordinary method that the described method vacuumizing is this area, does not repeat them here.
The lactic acid polymer that according to the present invention prepared by aforesaid method.
The invention will be further described by the following examples.
In following examples, the weight-average molecular weight of polymkeric substance and molecular weight distribution coefficient are according to gel permeation chromatography (GPC), take tetrahydrofuran (THF) (THF) as solvent, at Waters-208(band Waters 2410RI detector, 1.5ml/min flow velocity, 30 ℃) to measure on instrument, molecular weight is calibrated with vinylbenzene standard specimen;
(1) poly(lactic acid) endgroup content is measured by acetic anhydride room temperature acidylate method:
Accurately weigh fully dry poly-lactic acid products of about 2g left and right, be dissolved in 10mL methylene dichloride, add 1mL diacetyl oxide; 1mL pyridine; 30 ℃ of acetylizes 30 minutes, add afterwards 3-5 to drip the phenolphthalein/ethanolic soln of 1% concentration, be titrated to variable color with the NaOH/ ethanolic soln of 0.05mol/L.Use the same method and do blank assay to contrast.
Gained hydroxy radical content is calculated by following formula
Hydroxy radical content=(V
k-V
s) * C/m
In formula: V
kthe NaOH/ volumes of aqueous ethanol of the 0.05mol/L consuming during for blank test, unit is milliliter, V
sthe volume of the NaOH/ ethanolic soln of 0.05mol/L during for titration sample, unit is milliliter, and C is the actual concentrations of NaOH solution, and unit is mol/L, the quality that m is sample, unit is gram.
(2) monomer conversion adopts intermediate processing to measure:
Get after 1g sample, be dissolved in 10ml chloroform, then, by 100mL ethanol precipitation, filter and collect filtrate.By filtrate evaporate to dryness, measure lactide monomer residual volume.
Embodiment 1
The present embodiment is used for illustrating described lactic acid polymer of the present invention and preparation method thereof.
72.0 grams of 0.15 gram of 1-butylene alcohol, rac-Lactide are joined in polymerization bottle, be warmed up to 130 ℃, logical nitrogen deoxygenation, adds 0.048 gram, the sub-tin of octoate catalyst, keeps normal pressure, after 4 hours, reaches 80% by Precipitation Determination monomer conversion 170 ℃ of polymerizations.Add 0.5 gram of peroxidation (2-ethyl acid) tert-butyl ester at 170 ℃, 3.0 grams of methyl methacrylates, stir, continuing reaction 30 minutes, after reaction finishes, is to remove unreacted monomer under 2000Pa at pressure, product extruding pelletization, obtains lactic acid polymer P1.The number-average molecular weight of this P1 is 151 800, and molecular weight distribution is 3.40, and terminal hydroxyl content is 0.0363mmol/g.
Embodiment 2
Embodiment is used for illustrating described lactic acid polymer of the present invention and preparation method thereof.
150.0 grams of 0.15 gram of 1-butylene alcohol, rac-Lactide are joined in polymerization bottle, be warmed up to 130 ℃, logical nitrogen deoxygenation, adds 0.015 gram, the sub-tin of octoate catalyst,, after 200 ℃ of polymerase 10 .5 hours, reach 85% by Precipitation Determination monomer conversion.Adding 0.6 gram of peroxidation (2-ethyl acid) tert-butyl ester at 200 ℃, stir, is under 2000Pa, to continue reaction 90 minutes at pressure, after reaction finishes, is to remove unreacted monomer under 1000Pa at pressure, and product extruding pelletization, obtains lactic acid polymer P1.The number-average molecular weight of this P2 is 171 300., and molecular weight distribution is 3.10, and terminal hydroxyl content is 0.0297m mol/g.
Embodiment 3
The present embodiment is used for illustrating described lactic acid polymer of the present invention and preparation method thereof.
0.15 gram of 1-butylene alcohol, rac-Lactide 60.0 are joined in polymerization bottle, be warmed up to 130 ℃, logical nitrogen deoxygenation, adds 0.12 gram, the sub-tin of octoate catalyst, keeps normal pressure, at 180 ℃ of polyase 13s hour, reach 90% by Precipitation Determination monomer conversion, added 0.6 gram of 2,2-bis-(t-butyl peroxy) butane, 2,000 3.0 grams of hydroxy-terminated polybutadieness, stir the lower reaction 30 minutes that continues.After reaction finishes, be to remove unreacted monomer under 2000Pa at pressure, product extruding pelletization, obtains lactic acid polymer P3.The number-average molecular weight of this P3 is 224 600, and molecular weight distribution is 2.20, and terminal hydroxyl content is 0.0407m mol/g.
Embodiment 4
The present embodiment is used for illustrating described lactic acid polymer of the present invention and preparation method thereof.
0.15 gram of vinyl carbinol, rac-Lactide 72.0 are joined in polymerization bottle, be warmed up to 130 ℃, logical nitrogen deoxygenation, adds 0.04 gram, the sub-tin of octoate catalyst, keeps normal pressure, after 4 hours, has reached 82% by Precipitation Determination monomer conversion 170 ℃ of polymerizations.Add 0.6 gram of 2,2-bis-(t-butyl peroxy) butane at 170 ℃, 3.0 grams of methyl methacrylates, stir the lower reaction 60 minutes that continues.After reaction finishes, be to remove unreacted monomer under 2000Pa at pressure, product extruding pelletization, obtains lactic acid polymer P4.The number-average molecular weight of this P4 is 265 300, and molecular weight distribution is 200, and terminal hydroxyl content is 0.0117mmol/g.
Embodiment 5
The present embodiment is used for illustrating described lactic acid polymer of the present invention and preparation method thereof.
By 1,72.0 grams of 0.18 gram of 2-epoxy-5-hexenes, rac-Lactide join in polymerization bottle, are warmed up to 130 ℃, logical nitrogen deoxygenation, add 0.04 gram, the sub-tin of octoate catalyst, keep normal pressure, after 4 hours, reached 82% by Precipitation Determination monomer conversion 170 ℃ of polymerizations, add 2 at 170 ℃, 0.6 gram of 2-bis-(t-butyl peroxy) butane, 3.0 grams of vinylbenzene, stir the lower reaction 30 minutes that continues.After reaction finishes, be to remove unreacted monomer under 1000Pa at pressure, product extruding pelletization, obtains lactic acid polymer P5.The number-average molecular weight of this P5 is 156 000, and molecular weight distribution is 2.50, and terminal hydroxyl content is 0.0412mmol/g.
Embodiment 6
The present embodiment is used for illustrating described lactic acid polymer of the present invention and preparation method thereof.
72.0 grams of 0.18 gram of 1-butylene alcohol, rac-Lactide are joined in polymerization bottle, be warmed up to 130 ℃, logical nitrogen deoxygenation, adds 0.072 gram, the sub-tin of octoate catalyst, keep normal pressure, 170 ℃ of polymerizations, after 4 hours, Precipitation Determination monomer conversion has reached 75% monomer conversion and has reached 80% excessively, adds 2,0.6 gram of 2-bis-(t-butyl peroxy) butane, 3.0 grams of methacrylic acid stearyl, stir, and continue reaction 30 minutes.After reaction finishes, be to remove unreacted monomer under 1000Pa at pressure, product extruding pelletization, obtains lactic acid polymer P6.The number-average molecular weight of this P6 is 140 800, and molecular weight distribution is 3.40, and terminal hydroxyl content is 0.0212m mol/g.
Embodiment 7
The present embodiment is used for illustrating described lactic acid polymer of the present invention and preparation method thereof.
By 0.15 gram of glytidyl methacrylate, 72.0 grams of rac-Lactides, 11.4 grams of caprolactones join in polymerization bottle, are warmed up to 130 ℃, logical nitrogen deoxygenation, add 0.04 gram, the sub-tin of octoate catalyst, keep normal pressure,, after 4 hours, cross Precipitation Determination monomer conversion and reached 80% 170 ℃ of polymerizations, add 2,0.6 gram of 2-bis-(t-butyl peroxy) butane, 3.0 grams of methacrylic acid stearyl, stir the lower reaction 30 minutes that continues.After reaction finishes, be to remove unreacted monomer under 2000Pa at pressure, product extruding pelletization, obtains lactic acid polymer P6.The tuple average molecular weight of this P6 is 168 300, and molecular weight distribution is 2.80, and terminal hydroxyl content is 0.0252m mol/g.
Comparative example 1
Embodiment is for illustrating lactic acid polymer of prior art and preparation method thereof.
The basic embodiment 1 that repeats, difference is not add comonomer and radical initiator.72.0 grams of 0.15 gram of 1-butylene alcohol, rac-Lactide are joined in polymerization bottle, be warmed up to 130 ℃, logical nitrogen deoxygenation, adds 0.048 gram, the sub-tin of octoate catalyst, keeps normal pressure, after 4 hours, reaches 80% by Precipitation Determination monomer conversion 170 ℃ of polymerizations.After reaction finishes, be to remove unreacted monomer under 2000Pa at pressure, product extruding pelletization, obtains lactic acid polymer DP1.The number-average molecular weight of this DP1 is 121000, and molecular weight distribution is 2.10, and terminal hydroxyl content is 0.0021m mol/g.
Comparative example 2
Embodiment is for illustrating lactic acid polymer of prior art and preparation method thereof.
The basic embodiment 1 that repeats, difference is not add 1-butylene alcohol.72.0 grams of rac-Lactides are joined in polymerization bottle, be warmed up to 130 ℃, logical nitrogen deoxygenation, adds 0.048 gram, the sub-tin of octoate catalyst, keeps normal pressure, after 4 hours, reaches 80% by Precipitation Determination monomer conversion 170 ℃ of polymerizations.Add 0.5 gram of peroxidation (2-ethyl acid) tert-butyl ester, 3.0 grams of methyl methacrylates, stir, and continue reaction 30 minutes, after reaction finishes, are to remove unreacted monomer under 2000Pa at pressure, and product extruding pelletization, obtains lactic acid polymer DP2.The number-average molecular weight of this DP2 is 101 200, and molecular weight distribution is 5.10, and terminal hydroxyl content is 0.0037m mol/g.
The performance of the lactic acid polymer that embodiment 1-7 and comparative example 1-2 obtain is as shown in table 1 below.
Table 1
As can be seen from the table, the data of comparative example 1 and comparative example 1 are known, and the molecular weight of the lactic acid polymer of being prepared by embodiment 1 is higher, can have good processing characteristics; The concentration explanation of terminal hydroxy group, gained poly(lactic acid) terminal hydroxyl content is high, far above same molecular weight linear polymer, the branched polylactic acid that has obtained multiple end groups by present method is described, can form chain entanglement, has preferably processing characteristics.
Claims (12)
1. a preparation method for lactic acid polymer, the method comprises the following steps:
(1) under ring-opening polymerization condition, under rare gas element exists, monomer component containing rac-Lactide is contacted with ring-opening polymerization initiator with ring-opening polymerization catalyst, obtain lactide polymer, wherein, described ring-opening polymerization initiator is the unsaturated monohydroxy-alcohol that contains two keys and/or the epoxy compounds that contains two keys;
(2), under radical polymerization condition, the lactide polymer that step (1) is obtained and radical polymerization initiator contact reacts, obtain lactic acid polymer.
2. method according to claim 1, wherein, described ring-opening polymerization condition comprises that temperature is that 130-220 ℃, pressure are that 0-0.4MPa, time are 0.5-12 hour; Preferably, described temperature is that 170-200 ℃, pressure are that 0.07-0.1MPa, time are 0.5-4 hour.
3. method according to claim 1, wherein, the weight ratio of described ring-opening polymerization initiator, ring-opening polymerization catalyst and rac-Lactide is 1:0.05-1:200-1500.
4. according to the method described in claim 1 or 3, wherein, described ring-opening polymerization initiator is that carbonatoms is the unsaturated alcohol of 3-10 and/or the double bond containing epoxy compounds that carbonatoms is 3-10, more preferably one or more in vinyl carbinol, 1-butylene alcohol, 2-butylene alcohol, glytidyl methacrylate and 1,2-epoxy-5-hexene.
5. according to the method described in claim 1 or 3, wherein, described ring-opening polymerization catalyst is selected from one or more in stannous octoate, Dibutyltin oxide, titanic acid ester and aluminum isopropylate.
6. method according to claim 1, wherein, the method is also included in step (2), adds free yl polymerizating monomer.
7. method according to claim 6, wherein, in step (2), the weight ratio of described lactide polymer, radical polymerization initiator and free yl polymerizating monomer is 1000:0.05-5:1-50.
8. according to the method described in claim 6 or 7, wherein, described free yl polymerizating monomer is selected from one or more in acrylic ester monomer, styrene monomer, unsaturated fatty acids monomer, polyhutadiene and polyisoprene, is preferably one or more in hydroxy-terminated polybutadienes, vinylbenzene, methyl methacrylate and methacrylic acid stearyl.
9. according to the method described in any one in claim 1-8, wherein, described Raolical polymerizable condition comprises that temperature is that 150-220 ℃, pressure are that 0-0.4MPa, time are 15-180 minute; Preferably, described temperature is that 170-200 ℃, pressure are that 0.1-0.2MPa, time are 30-90 minute.
10. method according to claim 1, wherein, the described monomer component containing rac-Lactide also contains monomer c, and described monomer c is selected from least one in glycollide, caprolactone, butyrolactone, PDO, ring-type mutual-phenenyl two acid bromide two alcohol ester's oligopolymer and cyclic carbonate.
11. methods according to claim 1, wherein, described radical polymerization initiator is peroxide initiator, be preferably one or more in peroxidation (2 ethyl hexanoic acid) tert-butyl ester, isopropyl benzene hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, peroxidized t-butyl perbenzoate and 2,2-bis-(t-butyl peroxy) butane.
The lactic acid polymer that in 12. 1 kinds of claim 1-11, described in any one prepared by method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629020A (en) * | 2015-01-23 | 2015-05-20 | 常州大学 | Method for synthesizing macromonomer |
| CN105170064A (en) * | 2015-09-17 | 2015-12-23 | 河南天仁生物材料研究所有限公司 | High-viscosity polymerization plant and method for producing polylactic acid by using same |
| CN105273148A (en) * | 2014-07-24 | 2016-01-27 | 允友成(宿迁)复合新材料有限公司 | Preparation method of thermosetting polylactic acid |
-
2012
- 2012-10-30 CN CN201210424998.9A patent/CN103788313A/en active Pending
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105273148A (en) * | 2014-07-24 | 2016-01-27 | 允友成(宿迁)复合新材料有限公司 | Preparation method of thermosetting polylactic acid |
| CN104629020A (en) * | 2015-01-23 | 2015-05-20 | 常州大学 | Method for synthesizing macromonomer |
| CN105170064A (en) * | 2015-09-17 | 2015-12-23 | 河南天仁生物材料研究所有限公司 | High-viscosity polymerization plant and method for producing polylactic acid by using same |
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Application publication date: 20140514 |