CN101759969A - Polylactic acid composition and molding product thereof - Google Patents
Polylactic acid composition and molding product thereof Download PDFInfo
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- CN101759969A CN101759969A CN200810243806A CN200810243806A CN101759969A CN 101759969 A CN101759969 A CN 101759969A CN 200810243806 A CN200810243806 A CN 200810243806A CN 200810243806 A CN200810243806 A CN 200810243806A CN 101759969 A CN101759969 A CN 101759969A
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Abstract
The invention discloses a polylactic acid composition and a molding product thereof. The composition is mainly formed by the following components in part by weight: 100 parts of polylactic acid resin, 0.1 to 5 parts of an end blocking agent and 0.05 to 5 parts of a metal salt buffering agent. The composition and the molding product have high hydrolysis resistance; and compared with polylactic acid which is modified by purely using carbodiimide, the polylactic acid composition combines the buffering agent with the end blocking agent to obtain better hydrolysis resistance, can reduce the use amount of the carbodiimide, has the advantages of low cost and small toxicity, reduces the viscosity increase of a fusant caused by the carbodiimide, and thus improves the machinability of the polymer.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of poly (lactic acid) composition, be specifically related to a kind of poly (lactic acid) composition with excellent in resistance hydrolysis properties and goods thereof that contain end-capping reagent and buffering salt.
Background technology
Poly(lactic acid) is the polymkeric substance that obtains for the main raw material polymerization with lactic acid, and raw material sources fully and can regenerate.The production process of poly(lactic acid) is pollution-free, and product can biological degradation, is implemented in the circulation of occurring in nature, is the ideal green macromolecular material therefore.
Yet, poly-lactic acid material under hot and humid condition during long-time the exposure because the hydrolytic deterioration of polymer chain and can not keep the physicals of material fully.The hydrolytic resistance of improving poly (lactic acid) composition seems extremely important and necessary to adapt to the application that more and more widely reaches under the severe condition.
People know that the hydrolytic deterioration of polylactic resin is owing to the ester bond in the water molecules attack polylactic acid molecule causes the polymer chain break, and the end carboxyl on the polylactic acid molecule chain can quicken the hydrolytic cleavage of ester bond again.Therefore, by the content of carboxyl end group of control polylactic resin, can improve the stability to hydrolysis of poly-lactic acid material.The improvement of poly-lactic acid material hydrolysis characteristic can realize by adding the carbodiimide compounds usually.
Chinese invention patent 02124938.5 discloses a kind of fastener product of synthetic resins manufacturing of hydrolysis.It adds aromatic polycarbodiimide and realizes in vibrin.It is said that the fastener product of manufacturing has the excellent damp and hot weather resistance of resisting, and can keep stable bonding state, and do not produce such as defectives such as intensity reduction and variable colors.
It is the anti-method for hydrolysis of main body plastics that Japanese Patent JP9296097 discloses a kind of polyester (such as urethane, PET, poly(lactic acid) or the like).It is to add the stablizer of special carbodiimide as hydrolysis in the plastics of main body at polyester.Have good consistency between filler and main body, make filler well be dispersed in the resin, the matrix material that finally obtains has outstanding resistance to hydrolysis energy.
In Japanese Patent JP2001-261797, disclose and passed through with the C-terminal end-blocking of specific carbodiimide compound with poly(lactic acid), thus the technology of raising hydrolytic resistance.
Yet, as above-mentioned three invention, just merely with carbodiimide compound with poly(lactic acid) ground end-capped, have following shortcoming: at first be in order to improve hydrolytic resistance, too much use carbodiimide, to bringing burden on the product cost, cause melt viscosity increase in the course of processing in addition, give processing such as injection moulding, foaming, blowing brings difficulty, and the carbodiimide poor heat stability, produces the deleterious smell of HUMAN HEALTH.
Summary of the invention
The objective of the invention is to address the above problem,, improved above-mentioned weak point, thereby a kind of poly (lactic acid) composition with remarkable hydrolysis characteristic is provided by in polylactic resin and with buffer reagent and end group end-blocking.
Another object of the present invention is to provide a kind of moulding product of above-mentioned poly (lactic acid) composition preparation.
Purpose of the present invention can reach by following measure:
A kind of poly (lactic acid) composition mainly is made up of following components in part by weight: 100 parts of polylactic resin, 0.1～5 part of end-capping reagent, 0.05～5 part of metal-salt buffer reagent; Promptly mainly be 0.1～5% end-capping reagent of weight basis by poly(lactic acid), with the poly(lactic acid) and be that 0.05～5% metal-salt buffer reagent of weight basis is formed with the poly(lactic acid).Poly (lactic acid) composition of the present invention is except above-mentioned main component, still can add other known additive, for example, softening agent, thermo-stabilizer, antioxidant, photostabilizer, lubricant, tinting material, various mineral filler, fire retardant, crystallization nucleating agent.Poly (lactic acid) composition of the present invention also can only be made up of above-mentioned three kinds of main components.
The softening agent that can add in the composition of the present invention comprises: polyglycolic acid, polyvinyl acetate, one or more mixtures in polycaprolactone, ethylene oxide/propylene oxide multipolymer, the citrate.
The polylactic resin that the present invention adopts is poly (l-lactic acid), poly-D-lactic acid or poly-DL-lactic acid or both above blends; Perhaps poly (l-lactic acid) gathers both above multipolymers in D-lactic acid, the poly-DL-lactic acid; Perhaps poly (l-lactic acid), the blend of both above multipolymers in poly-D-lactic acid, the poly-DL-lactic acid.
As the polymerization process of polylactic acid polymer, can use the polycondensation method, known method such as ring-opening polymerization method.And described polymkeric substance weight-average molecular weight is 5～50w, wherein preferred 10～30w.
In poly (lactic acid) composition, end-capping reagent is selected from one or more of carbodiimide compound, epoxy compounds, oxazoline compound (such as bisoxazoline), oxazine compound, aziridine cpd, wherein preferred carbodiimide compound.
The carbodiimide compound object lesson can be N, N '-two-2,6-diisopropylbenzene(DIPB) carbodiimide, N, N '-two-o-tolyl carbodiimide, N, N '-hexichol carbodiimide, N, N '-two-octadecane carbodiimide, N, N '-two-2,6-dimethylbenzene carbodiimide, N-tolyl-N '-cyclohexyl carbodiimide, N, N '-two-2,6-two-trimethylphenylmethane carbodiimide, N-tolyl-N '-benzene carbodiimide, N, N '-two-p-nitrophenyl carbodiimide, N, N '-two-p-aminophenyl carbodiimide, N, N '-two-para hydroxybenzene carbodiimide, N, N '-two-cyclohexyl carbodiimide, N, N '-two-p-methylphenyl carbodiimide, to phenylene-two two-o-tolyl carbodiimide, to phenylene-two-dicyclohexyl carbodiimide, hexa-methylene-two-dicyclohexyl carbodiimide, 4,4 '-dicyclohexyl methyl hydride carbodiimide, ethylidene-two-hexichol carbodiimide, N, N '-benzyl carbodiimide, N-octadecyl-N '-benzene carbodiimide, N-benzyl-N '-benzene carbodiimide, N-octadecyl-N '-tolyl carbodiimide, N-cyclohexyl-N '-tolyl carbodiimide, N-phenyl-N '-tolyl carbodiimide, N-benzyl-N '-tolyl carbodiimide, N, the adjacent ethylphenyl carbodiimide of N '-two, N, N '-two pair of ethylphenyl carbodiimide, N, the adjacent cumyl carbodiimide of N '-two, N, N '-two pair of cumyl carbodiimide, N, the adjacent isobutylphenyl carbodiimide of N '-two, N, N '-two pair of isobutylphenyl carbodiimide, N, N '-two-2,6-diethyl phenyl carbodiimide, N, N '-two-2-ethyl-6-cumyl carbodiimide, N, N '-two-2-isobutyl--6-cumyl carbodiimide, N, N '-two-2,4,6-trimethylphenyl carbodiimide, N, N '-two-2,4,6-tri-isopropyl benzene base carbodiimide, N, N '-two-2,4,6-three isobutylphenyl carbodiimide, the di-isopropyl carbodiimide, the dimethyl carbodiimide, the diisobutyl carbodiimide, the dioctyl carbodiimide, tertiary butyl sec.-propyl carbodiimide, two-betanaphthyl carbodiimide, two-tertiary butyl carbodiimide, aromatic polycarbodiimide etc.And then can enumerate the polymkeric substance of these compounds.Can use these carbodiimide compounds separately, also can two or more be used in combination.
The carbodiimide compound that the present invention preferably adopts, its melting range are 35 ℃～45 ℃.
The metal-salt buffer reagent comprises water miscible metal organic acid salt (as Sodium Benzoate) or metal inorganic Barbiturates, and wherein preferable alloy inorganic phosphate salt buffer agent specifically is selected from NaH
2PO
4, Na
2HPO
4, K
2HPO
4, KH
2PO
4, Na
2HPO
3, K
2HPO
3, NaH
2PO
2, KH
2PO
2, Ca
3(PO
4)
2, Ca (H
2PO
2)
2, CaHPO
4Or among the CaHPOX one or more.
A kind of moulding product of poly (lactic acid) composition, with above-mentioned poly (lactic acid) composition melt blending after overmolding processing make.The forming process means are as extruding injection moulding, foaming, blowing, curtain coating, mold pressing etc.
Beneficial effect of the present invention: have preferable hydrolytic resistance via poly (lactic acid) composition of the present invention, this advantage reduces degree by composition particle molecular weight before and after thermostatic constant wet chamber's hydrolysis and seldom confirms, in addition, compare with the poly(lactic acid) of simple use carbodiimide modification, buffer reagent and end-capping reagent are also with obtaining better hydrolysis effect, and can reduce the carbodiimide usage quantity, it is low to have cost, the advantage that toxicity is little, and in the course of processing, reduced the melt viscosity increase that carbodiimide causes, improved the processability of polymkeric substance thus.
Embodiment
For further specifying purpose of the present invention, feature and advantage, illustrated below by specific embodiment.
Hydrolysising condition and molecular weight determination:
The hydrolysising experiment of poly(lactic acid): the poly(lactic acid) particle is put into 40 ℃ of temperature, and in the thermostatic constant wet chamber of relative humidity 90%, hydrolysis time was followed successively by 0 day, and 6 days, 20 days.Hydrolysis is treated to keep well after the pellet drying after finishing.
Molecular weight determination: get 15～20mg pellet with after the tetrahydrofuran (THF) dissolving, carry out GPC (Tianjin, island) test.30 ℃ of column temperatures, flow velocity 1.0000ml/min, each sample experimental period 35min.Obtain number-average molecular weight Mn at last, weight-average molecular weight Mw, and data such as molecular weight distribution mw/mn.
Embodiment 1
With 90 parts of polylactic resin (4032D, Nature works company, weight-average molecular weight 18～22w), 10 parts of (tributyl citrate) total amount 500g of softening agent and account for the KH of the two weight 0.05%
2PO
4, account for carbodiimide (the stabaxol 1LF of the two weight 1%, the TUV chemistry, 40～45 ℃ of fusing points) and account for the crystallization nucleating agent of the two weight 1% (3988, Mei Lide) blend is carried out melt blending by twin screw extruder and extruded, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 1.
Embodiment 2
With 90 parts of polylactic resin (4032D, Nature works company, weight-average molecular weight 18～22w), 10 parts of (tributyl citrate) total amount 500g of softening agent and account for the KH of the two weight 2%
2PO
4, account for carbodiimide (the stabaxol 1LF of the two weight 1%, the TUV chemistry, 40～45 ℃ of fusing points) and account for the crystallization nucleating agent of the two weight 1% (3988, Mei Lide) blend is carried out melt blending by twin screw extruder and extruded, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 1.
Embodiment 3
With 90 parts of polylactic resin (4032D, Nature works company, weight-average molecular weight 18～22w), 10 parts of (tributyl citrate) total amount 500g of softening agent and account for the KH of the two weight 4%
2PO
4, account for carbodiimide (the stabaxol 1LF of the two weight 1%, the TUV chemistry, 40～45 ℃ of fusing points) and account for the crystallization nucleating agent of the two weight 1% (3988, Mei Lide) blend is carried out melt blending by twin screw extruder and extruded, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 1.
Comparative Examples 1
With 90 parts of (4032D of polylactic resin, Nature works company, weight-average molecular weight 18～22w), 10 parts of (tributyl citrate) total amount 500g of softening agent and carbodiimide (the stabaxol 1LF that accounts for the two weight 1%, the TUV chemistry, 40～45 ℃ of fusing points) and the crystallization nucleating agent (3988 that accounts for the two weight 1%, Mei Lide) blend, carrying out melt blending by twin screw extruder extrudes, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 1.
Molecular weight change list before and after table 1 hydrolysis experiment
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Contrast 1 | |
| 4032/ softening agent | ??90/10 | ??90/10 | ??90/10 | ??90/10 |
| ??KH 2PO 4 | ??0.2％ | ??2％ | ??4％ | ??- |
| ??Stab?1LF | ??1％ | ??1％ | ??1％ | ??1％ |
| ??3988 | ??1％ | ??1％ | ??1％ | ??1％ |
| Hydrolysis 0 day | ??208.1 | ??199.6 | ??208.3 | ??204.5 |
| Hydrolysis 6 days | ??187.5 | ??185.2 | ??188.3 | ??174.4 |
| Hydrolysis 20 days | ??131.1 | ??149.3 | ??164.5 | ??101.0 |
Embodiment 4
With polylactic resin (6251D, Nature works company, weight-average molecular weight 7～13w) 100 weight part 500g and the Na that accounts for PLA (polylactic resin) weight 1%
2HPO
4, 1% KH
2PO
4And the dicyclohexyl carbodiimide (DCC that accounts for PLA weight 0.5%, the Shanghai covalent chemical, 32～35 ℃ of fusing points) blend, carry out melt blending by twin screw extruder and extrude, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 2.
Embodiment 5
With polylactic resin (6251D, Nature works company, weight-average molecular weight 7～13w) 100 weight part 500g and the Na that accounts for PLA (polylactic resin) weight 1%
2HPO
4, 1% KH
2PO
4And the dicyclohexyl carbodiimide (DCC that accounts for PLA weight 2%, the Shanghai covalent chemical, 32～35 ℃ of fusing points) blend, carry out melt blending by twin screw extruder and extrude, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 2.
Embodiment 6
With polylactic resin (6251D, Nature works company, weight-average molecular weight 7～13w) 100 weight part 500g and the Na that accounts for PLA (polylactic resin) weight 1%
2HPO
4, 1% KH
2PO
4And the dicyclohexyl carbodiimide (DCC that accounts for PLA weight 4%, the Shanghai covalent chemical, 32～35 ℃ of fusing points) blend, carry out melt blending by twin screw extruder and extrude, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 2.
Comparative Examples 2
With polylactic resin (6251D, Nature works company, weight-average molecular weight 7～13w) 100 weight part 500g and the Na that accounts for PLA (polylactic resin) 1%
2HPO
4, 1% KH
2PO
4Blend is carried out melt blending by twin screw extruder and is extruded, and melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 2.
Molecular weight change list before and after table 2 hydrolysis experiment
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Contrast 2 | |
| ??DCC | ??0.5％ | ??2％ | ??4％ | ??- |
| ??Na 2HPO 4 | ??1％ | ??1％ | ??1％ | ??1％ |
| ??KH 2PO 4 | ??1％ | ??1％ | ??1％ | ??1％ |
| Hydrolysis 0 day | ??100.1 | ??105.6 | ??108.9 | ??112.3 |
| Hydrolysis 6 days | ??86.3 | ??93.4 | ??95.1 | ??74.3 |
| Hydrolysis 20 days | ??42.2 | ??74.5 | ??78.5 | ??35.6 |
Embodiment 7
With polylactic resin (REVODE 101, and the positive biotech firm in sea is about weight-average molecular weight 20w) 100 weight part 500g and the CaHPO that accounts for PLA (polylactic resin) weight 0.4%
4And carbodiimide (the stabaxol 1LF that accounts for PLA weight 0.5%, the TUV chemistry) and account for the epoxy compounds (MP20 of PLA weight 1%, Japan is spun clearly day) blend, carry out melt blending by twin screw extruder and extrude, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 3.
Embodiment 8
With polylactic resin (REVODE 101, and the positive biotech firm in sea is about weight-average molecular weight 20w) 100 weight part 500g and the CaHPO that accounts for PLA (polylactic resin) weight 1%
4And carbodiimide (the stabaxol 1LF that accounts for PLA weight 2%, the TUV chemistry) and account for the epoxy compounds (MP20 of PLA weight 1%, Japan is spun clearly day) blend, carry out melt blending by twin screw extruder and extrude, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 3.
Embodiment 9
With polylactic resin (REVODE 101, and the positive biotech firm in sea is about weight-average molecular weight 20w) 100 weight part 500g and the CaHPO that accounts for PLA (polylactic resin) weight 3%
4And carbodiimide (the stabaxol 1LF that accounts for PLA weight 4%, the TUV chemistry) and account for the epoxy compounds (MP20 of PLA weight 1%, Japan is spun clearly day) blend, carry out melt blending by twin screw extruder and extrude, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 3.
Comparative Examples 3
(REVODE 101 with polylactic resin, the positive biotech firm in sea, about weight-average molecular weight 20w) 100 weight part 500g and carbodiimide (the stabaxol 1LF that accounts for PLA weight 1%, the TUV chemistry) and account for the epoxy compounds (MP20 of PLA weight 1%, Japan is spun clearly day) blend, carrying out melt blending by twin screw extruder extrudes, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 3.
Molecular weight change list before and after table 3 hydrolysis experiment
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Contrast 3 | |
| ??CaHPO 4 | ??0.4％ | ??1％ | ??3％ | ??- |
| ??1LF | ??0.5％ | ??2％ | ??4％ | ??1％ |
| ??MP20 | ??1％ | ??1％ | ??1％ | ??1％ |
| Hydrolysis 0 day | ??208.1 | ??198.4 | ??207.0 | ??208.1 |
| Hydrolysis 6 days | ??171.3 | ??177.4 | ??187.0 | ??175.4 |
| Hydrolysis 20 days | ??100.2 | ??131.3 | ??160.9 | ??112.3 |
Embodiment 10
With polylactic resin (4042D, Nature works company, weight-average molecular weight 18～22w) 100 weight part 500g with account for the Sodium Benzoate of PLA (polylactic resin) weight 1% and account for PLA weight 1% De bisoxazoline (Dalian chemical research institute) blend, carrying out melt blending by twin screw extruder extrudes, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 4.
Embodiment 11
With polylactic resin (4042D, Nature works company, weight-average molecular weight 18～22w) 100 weight part 500g with account for the Sodium Benzoate of PLA (polylactic resin) weight 3% and account for PLA weight 1% De bisoxazoline (Dalian chemical research institute) blend, carrying out melt blending by twin screw extruder extrudes, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 4.
Embodiment 12
With polylactic resin (4042D, Nature works company, weight-average molecular weight 18～22w) 100 weight part 500g with account for the Sodium Benzoate of PLA (polylactic resin) weight 5% and account for PLA weight 1% De bisoxazoline (Dalian chemical research institute) blend, carrying out melt blending by twin screw extruder extrudes, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 4.
Comparative Examples 4
With polylactic resin (4042D, Nature works company, weight-average molecular weight 18～22w) 100 weight part 500g with account for PLA weight 1% De bisoxazoline (Dalian chemical research institute) blend, carry out melt blending by twin screw extruder and extrude, melt is through tank cooling back granulation, 180 ℃ of forcing machine feed zone temperature, second section 190 ℃, all the other sections are 200 ℃, and with dry 4 hours of particle, the molecular weight of analyzing then before and after the gained pellet hydrolysis experiment changed.The result is as shown in table 4.
Molecular weight change list before and after table 4 hydrolysis experiment
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Contrast 4 | |
| Sodium Benzoate | ??1％ | ??3％ | ??5％ | ??- |
| Bisoxazoline | ??1％ | ??1％ | ??1％ | ??1％ |
| Hydrolysis 0 day | ??215.6 | ??200.5 | ??224.6 | ??196.0 |
| Hydrolysis 6 days | ??163.0 | ??176.3 | ??188.6 | ??170.1 |
| Hydrolysis 20 days | ??99.5 | ??133.2 | ??167.3 | ??124.3 |
As can be seen from the above embodiments, less by molecular weight and molecular weight after the poly (lactic acid) composition hydrolysis of end-capping reagent, the common modification of buffer reagent, modified effect even surpass the simple carbodiimide compound modification of using.According to above content, proved that the poly (lactic acid) composition among the present invention has preferable hydrolytic resistance.
Claims (9)
1. a poly (lactic acid) composition is characterized in that, mainly is made up of following components in part by weight:
100 parts of polylactic resin
0.1～5 part of end-capping reagent
0.05～5 part of metal-salt buffer reagent.
2. poly (lactic acid) composition according to claim 1 is characterized in that, the weight-average molecular weight of described polylactic resin is 5～50w.
3. poly (lactic acid) composition according to claim 2 is characterized in that, the weight-average molecular weight of described polylactic resin is 10～30w.
4. poly (lactic acid) composition according to claim 1 is characterized in that, described end-capping reagent is selected from one or more of carbodiimide compound, epoxy compounds, oxazoline compound, oxazine compound or aziridine cpd.
5. poly (lactic acid) composition according to claim 4 is characterized in that, described end-capping reagent is a carbodiimide compound.
6. poly (lactic acid) composition according to claim 1 is characterized in that, described metal-salt buffer reagent is water miscible metal organic acid salt buffer reagent or metal inorganic Barbiturates buffer reagent.
7. poly (lactic acid) composition according to claim 6 is characterized in that, described metal-salt buffer reagent is a metal inorganic phosphoric acid salt buffer reagent.
8. poly (lactic acid) composition according to claim 7 is characterized in that, described metal inorganic Barbiturates buffer reagent is selected from NaH
2PO
4, Na
2HPO
4, K
2HPO
4, KH
2PO
4, Na
2HPO
3, K
2HPO
3, NaH
2PO
2, KH
2PO
2, Ca
3(PO
4)
2, Ca (H
2PO
2)
2, CaHPO
4Or CaHPO
3In one or more.
9. the moulding product by the described poly (lactic acid) composition preparation of claim 1 is characterized in that, moulding obtains through the melt blending post-treatment.
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|---|---|---|---|
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| US20120261299A1 (en) * | 2011-04-12 | 2012-10-18 | Basf Se | Oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound |
| WO2012140561A1 (en) * | 2011-04-12 | 2012-10-18 | Basf Se | Oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound |
| US9982128B2 (en) | 2013-09-30 | 2018-05-29 | 3M Innovative Properties Company | Fibers, wipes, and methods |
| US10006165B2 (en) | 2013-09-30 | 2018-06-26 | 3M Innovative Properties Company | Fibers and wipes with epoxidized fatty ester disposed thereon, and methods |
| CN115029812A (en) * | 2022-06-02 | 2022-09-09 | 南通大学 | Degradation-controllable polylactic acid fiber and preparation method and application thereof |
| WO2022195041A1 (en) | 2021-03-17 | 2022-09-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Stabilizer composition, use of the stabilizer composition, method for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molded part consisting thereof |
| WO2024002610A1 (en) | 2022-06-27 | 2024-01-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Stabiliser composition, use of the stabiliser composition, method for stabilising condensation polymers against hydrolytic degradation, and hydrolysis-stabilised composition and moulding or moulded part consisting thereof |
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2008
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| US20120261299A1 (en) * | 2011-04-12 | 2012-10-18 | Basf Se | Oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound |
| WO2012140561A1 (en) * | 2011-04-12 | 2012-10-18 | Basf Se | Oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound |
| US9023931B2 (en) | 2011-04-12 | 2015-05-05 | Basf Se | Oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound |
| US9982128B2 (en) | 2013-09-30 | 2018-05-29 | 3M Innovative Properties Company | Fibers, wipes, and methods |
| US10006165B2 (en) | 2013-09-30 | 2018-06-26 | 3M Innovative Properties Company | Fibers and wipes with epoxidized fatty ester disposed thereon, and methods |
| WO2022195041A1 (en) | 2021-03-17 | 2022-09-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Stabilizer composition, use of the stabilizer composition, method for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molded part consisting thereof |
| DE102021202598A1 (en) | 2021-03-17 | 2022-09-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Stabilizer composition, use of the stabilizer composition, process for stabilizing condensation polymers against hydrolytic degradation, and hydrolysis-stabilized composition and molding or molding made therefrom |
| CN115029812A (en) * | 2022-06-02 | 2022-09-09 | 南通大学 | Degradation-controllable polylactic acid fiber and preparation method and application thereof |
| WO2024002610A1 (en) | 2022-06-27 | 2024-01-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Stabiliser composition, use of the stabiliser composition, method for stabilising condensation polymers against hydrolytic degradation, and hydrolysis-stabilised composition and moulding or moulded part consisting thereof |
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