CN102718947B - Novel polyhydroxyalkanoate and preparation method of novel polyhydroxyalkanoate - Google Patents
Novel polyhydroxyalkanoate and preparation method of novel polyhydroxyalkanoate Download PDFInfo
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Abstract
The invention relates to a method for preparing polyhydroxyalkanoate and polyhydroxyalkanoate prepared by the preparation method. According to the method, lewis acid is used as catalysts, hydracarboxylic acid ester monomers are subjected to solid phase polymerization reaction, polyhydroxycarboxylic acid low polymers are obtained, and then, the polyhydroxycarboxylic acid low polymers are crushed under the protection of inert gas; and finally, under the conditions that the pressure is 10 Pa to 100 Pa, and the temperature is 100 to 250 DEG C, the reaction is carried out for 10 to 300 hours, and the polyhydroxyalkanoate is obtained. The polyhydroxyalkanoate has the advantages that the degradation rate is low, and the hot melt viscosity is high.
Description
Technical field
The present invention relates to a kind of biodegradable polyhydroxycarboxyliacid acid ester and preparation method thereof.
Technical background
Traditional macromolecular material is general all from non-renewable petroleum resources, and is difficult to degraded.Although play irreplaceable effect in the socio-economic development process, face white pollution and energy starved problem.
The polyhydroxycarboxyliacid acid ester, for example, poly butyric ester (PHB) is a kind of polyester extensively existed in bacterial body, has the physicochemical characteristic and the biodegradability that are similar to chemical plastic, part is used as the plastics of environmentally degradable and is applied.And polyhydroxyalkanoate also has the performances such as biocompatibility, optical activity, piezoelectricity and being separated by property of gas, also can be used widely in fields such as medical treatment, electronics.
The polyhydroxycarboxyliacid acid ester is mainly by biosynthesizing at present, and the mode of fermenting by microorganism is synthetic.But microorganism fermentative production polyhydroxycarboxyliacid acid ester can cause the environment such as soil, water to be subject to substantial pollution, and also need special fermentation equipment in production process, fermenting process needs strict control, the invisible production cost that increased to the factors such as pollution of temperature and bacterial classification.
The biological degradation rate of polyhydroxycarboxyliacid acid ester is often too fast, when making film or container etc. and be applied to field that weather resistance and profile keep, can cause that article intensity descends too early and makes and be difficult to keep for a long time the article profile.
Therefore, need a kind of low polyhydroxycarboxyliacid acid ester material of degradation rate, and a kind of simple, easy-operating, be applicable to the industrialized synthetic method for preparing the polyhydroxycarboxyliacid acid ester.
Summary of the invention
The purpose of this invention is to provide a kind of method that simply by chemosynthesis, prepares the polyhydroxycarboxyliacid acid ester, described method comprises the following steps:
1) take Lewis acid as catalyzer, is 10-600KPa by hydroxycarboxylic acid esters monomer or hydroxy aliphatic acyl chlorides monomer at pressure, and polyreaction 1-10h under the condition that temperature is 80-230 ℃, obtain the polyhydroxycarboxyliacid acid ester oligomer; The 0.1-5.0% that described catalyst levels is hydroxycarboxylic acid esters monomer total mass; The 0.1-1.0% that preferred catalyst levels is the hydroxycarboxylic acid esters total mass.
2) the polyhydroxycarboxyliacid acid ester oligomer obtained under the protection of shielding gas, pulverising step 1).
3) by step 2) react 10-300h under the condition of oligopolymer solid phase polycondensation pressure 10Pa-100KPa, temperature 100-250 ℃ that obtains, obtain the polyhydroxycarboxyliacid acid ester.
Wherein said hydroxycarboxylic acid esters monomer comprises: hydroxyl group aliphatic carboxylicesters, such as methyl glycolate, ethyl glycollate, methyl lactate, ethyl lactate, butyl glycolate etc.; Or the hydroxy aliphatic acyl chlorides, such as glycoloyl chlorine, lactic acid acyl chlorides etc.; Preferably, methyl glycolate, ethyl glycollate, methyl lactate, ethyl lactate, glycoloyl chlorine, butyl glycolate or 4 hydroxybutyric acid methyl esters; More preferably methyl glycolate, methyl lactate, butyl glycolate or 4 hydroxybutyric acid methyl esters.
Described lewis acid catalyst is zinc, antimony, germanium, tin, titanyl compound or metal-salt, comprising: carboxylate salt, lime acetate, zinc acetate, two hydration zinc acetates, antimonous oxide, germanium dioxide, antimony trisulfide, tin protochloride, two hydrated stannous chlorides, stannous octoate, tin chloride, stannic oxide, chromic oxide, titanium dioxide, complexing Titanium series catalyst etc.Preferred two hydration zinc acetates, antimonous oxide, a kind of in two hydrated stannous chlorides, or two or more composite catalyst arbitrarily.
The consumption of catalyzer is larger on the productive rate impact of reaction, in contriver's research, finds, catalyst levels is 0.1～1.0% of hydroxycarboxylic acid esters total mass, can make the productive rate of polyhydroxycarboxyliacid acid ester reach more than 99%.
Described step (1) is according to the difference of hydroxycarboxylic acid esters monomer, suitable conditioned reaction condition, the step-down of preferable procedure intensification matching program.In reaction process, according to ordinary skill in the art means, the alcohol produced in reaction process can be isolated to reaction system, to promote the carrying out of polyreaction.
Described temperature programming, refer to according to fixing or revocable ratio rising temperature of reaction; Described program step-down, refer to according to fixing or revocable ratio and reduce pressure.
For example, take methyl glycolate during as raw material, under the condition that is preferably 80-120 ℃ or 150-190 ℃ in temperature of reaction, reacted by the mode of temperature programming; Under the condition that is more preferably 80-100 ℃ or 150-180 ℃ in temperature, carry out; Most preferably in the said temperature scope, with the speed of 5-10 ℃ of per hour the heating up control that heats up, and keep temperature of reaction more than 2 hours after heating up the last time; Preferably with the speed of 10 ℃ per hour, carry out temperature controlled.For example, isolate a large amount of methyl alcohol after mixing for some time in the time of 80 ℃, under 10-600KPa pressure, react after 1 hour and be warming up to 90 ℃ of reactions, maintain the temperature of reaction polymerization 2 hours after being warming up to again 100 ℃ after 1 hour.
When take butyl glycolate during as raw material, preferably in the temperature range of 180-190 ℃, under 10-600KPa pressure, carry out temperature control with the speed of 5-10 ℃ of per hour heating up, and keep temperature of reaction to carry out polyreaction more than 2 hours after heating up the last time.More preferably, in described temperature range, with the speed of 5 ℃, carry out temperature control.
When take the 4 hydroxybutyric acid methyl esters during as raw material, preferably in the temperature range of 210-230 ℃, under 10-600KPa pressure, with the speed of 5-10 ℃ of per hour heating up, carry out temperature control, and keep temperature of reaction to carry out polyreaction more than 2 hours after heating up the last time.More preferably, in described temperature range, with the speed of 10 ℃, carry out temperature control.
Described reaction pressure, can suitably reduce according to the rising of temperature in reaction.
Described step 2), preferably under the protection of nitrogen, carry out.Described pulverizing is ordinary skill in the art means, such as being pulverized by modes such as grindings.
Described step 3) is preferably carried out under the temperature condition of 100-180 ℃, more preferably under the temperature condition of 100 or 180 ℃, carries out.The preferred 50Pa-50KPa of described pressure, more preferably 70Pa-5Kpa.The described reaction times is preferably 20～250h, more preferably 40～200h.
The contriver finds in research process, there is great impact the time of the polyreaction in step 3) on the viscometric properties of polymkeric substance, the increase of solid phase polycondensation time, limiting viscosity first increases afterwards and reduces in a scope, the limiting viscosity of polyhydroxycarboxyliacid acid ester is 0.1018dL/g as shown in Figure 5, solid-phase tack producing 120h left and right, limiting viscosity reaches maximum value.In the increase along with the time, limiting viscosity starts to descend afterwards, and when the time increases to 200h, limiting viscosity drops to 0.4650dL/g.The preparation method of polyhydroxycarboxyliacid acid ester provided by the present invention, when the step 3) temperature of reaction is 40-200h, resulting polyhydroxycarboxyliacid acid ester has suitable range of viscosities, at 250 ℃ of viscosity (η that measure after keeping 60 minutes
60) with the initial viscosity (η of mensuration after 250 ℃ of preheatings 5 minutes
0) ratio [(η
60/ η
0) * 100], the melt viscosity retention rate is greater than 35%.Therefore the polyhydroxycarboxyliacid acid ester has better weather resistance and shape retention.
A preparation technology's of the present invention embodiment can be as follows:
Another aspect of the present invention provides a kind of by the above-mentioned polyhydroxycarboxyliacid acid ester that the direct solid phase polycondensation of hydroxycarboxylic acid esters is prepared: it is characterized in that described polyhydroxycarboxyliacid acid ester has:
(a) 10,000～1, the weight-average molecular weight (Mw) in 000,000 scope,
(b) when for molecular weight distribution, weight-average molecular weight/number-average molecular weight (Mw/Mn) is than value representation, be 0.8～3.0,
(c) when the sheet material that compression moulding and crystallization obtain is measured, yellowness index (YI) is up to 50,
(d) at 250 ℃ of viscosity (η that measure after keeping 60 minutes
60) with the initial viscosity (η of mensuration after 250 ℃ of preheatings 5 minutes
0) ratio [(η
60/ η
0) * 100], the melt viscosity retention rate is greater than 35%.
In the nitrogen gas stream that further described polyhydroxycarboxyliacid acid ester is 10ml/min at flow, with the heating rate of 2 ℃/min during from 50 ℃ of heating, temperature when its rate of weight loss in the time of 50 ℃ reaches 1% is 200 ℃ or higher;
Or/and the melt viscosity of described polyhydroxycarboxyliacid acid ester under the shearing rate of the temperature of 240 ℃ and 122/ second is 10～200,000Pas.
The preferred polyglycolic acid methyl esters of described polyhydroxycarboxyliacid acid ester, polyglycolic acid butyl ester or poly-4 hydroxybutyric acid methyl esters.
The invention provides a kind of polyhydroxycarboxyliacid acid ester material, and provide a kind of reaction of new chemosynthesis polyhydroxycarboxyliacid acid ester, by the creative research to reaction conditions, obtained and had the excellent polymkeric substance of melt stability, polymer viscosity is higher, and its intensity and profile can be kept, not too fast decline, and painted few, can directly as degradable plastics, use, extend the work-ing life of degradative plastics.And the method for preparing polymkeric substance also has high yield a little, applicable suitability for industrialized production.
The accompanying drawing explanation
The infared spectrum that Fig. 1 is the polyglycolic acid methyl esters for preparing of embodiment 1.
Fig. 2 is the polyglycolic acid methyl esters for preparing of embodiment 1
1the HNMR spectrogram.
The DSC curve that Fig. 3 is the polyglycolic acid methyl esters for preparing of embodiment 1.
The XRD spectra that Fig. 4 is the polyglycolic acid methyl esters for preparing of embodiment 1.
Prepared in the solid phase polycondensation process of polyglycolic acid methyl esters by Fig. 5, limiting viscosity is along with the variation collection of illustrative plates of time.
Embodiment
Following embodiment is to further illustrate of the present invention, rather than limits the scope of the invention.
Unless stated otherwise, raw material of the present invention and reagent and equipment, all can obtain by commercially available purchase.
Detection method of the present invention is ordinary skill in the art method:
Described infared spectrum, measure (KBr pressed disc method) by Fourier infrared spectrograph.
Described 1H-NMR with deuterium for trifluoroacetic acid (CF
3cOOD) be solvent, TMS is that interior mapping is fixed.
Described X-powdery diffractometry condition is: electric current 30mA, slit DS=SS=1 °, RS=0.3mm, 10 °/min of sweep velocity, graphite monochromator, copper target, 5 °～80 ° of sweep limits.
In the X-ray diagram, the ratio of crystal region area and the total area, be defined as degree of crystallinity (Crystallinity).With formula (a), calculate:
Degree of crystallinity=A
c/ (A
c+ A
a) * 100% (a)
Wherein: A
c---brilliant peak area A
a---the amorphous peak area
Described dsc analysis condition is: N
2flow velocity 40mL/min, since 50 ℃, be warmed up to 250 ℃ with 20 ℃/min, at 250 ℃, keeps 1.0min, then with 10 ℃/min, cools to 50 ℃.
Described limiting viscosity method is: accurately take the polymer beads of 25mg through grinding, be dissolved in containing in the hexafluoroisopropanol solution of 5mM sodium trifluoroacetate, under 25 ℃ of conditions, utilize 0.5～0.6mm caliber Ubbelohde viscometer to test out respectively the elution time t of neat solvent and polymers soln
0with the calculating of t limiting viscosity, by " one point method " formula, try to achieve:
[η]=[2(ησπ-λνηρ)]1/2/χ (β)
Wherein: η ρ=τ/τ 0 is relative viscosity; η σ π=η ρ-1 is specific viscosity
Each sample replicate(determination) 3 times, the elution time of each mensuration differs and can not surpass 0.2s.Finally, by 3 results averaged, be the elution time of liquid to be measured.
Described weight average average molecular flow measurement: sample dissolution, in the hexafluoroisopropanol solution that contains the 5mM sodium trifluoroacetate, is made into to 0.05～0.3%(massfraction) solution.Filter with teflon membrane filter, then get 20 η L and join in gel permeation chromatograph (GPC) sampler, use 5 kinds of different standard polymethylmethacrylates of molecular weight to carry out molecular weight calibration.
Described measuring melt viscosity: the 10g polyhydroxycarboxyliacid acid ester that will be clipped between aluminium sheet is placed on the press that is preheating to 240 ℃, after the 30s preheating, with 5MPa, presses 15s, then cooling to make a kind of sheet material rapidly.Amorphous sheet material like this heats the 15min crystallization in 150 ℃ in baking oven.Sampling 7g, put in the cylinder that Japan's upper internal diameter of the essence machine Capirograph3C processed of company is 9.55mm 240 ℃ of design temperatures.Preheating 5min, after by sample from internal diameter 1mm, the die head of length 1mm is extruded with the shearing rate of 122/ second, obtains the melt viscosity (Pas) of sample from stress now.
Described percent weight loss rate is measured: the TG50 that uses Metler company to manufacture, at a kind of nitrogen, in the nitrogen atmosphere leading with the fluence rate of 10ml/min, the heating rate with 2 ℃/min of polyglycolic acid is from 50 ℃ of heating.Sample is at the weight (W of 50 ℃
50) temperature that demonstrates 1% loss reads exactly.This paper defines the percent weight loss rate by this temperature and reaches 1% temperature.
Fig. 1 is the prepared polyglycolic acid methyl esters infrared spectrum of example 1, can find out 1746cm
-1place is polymer esters carbonyl C=O stretching vibration peak; 1154cm
-1and 1089cm
-1what locate is ester group C-O-C absorption peak; 3515cm
-1place is polymer ends hydroxyl-OH absorption peak.2993cm
-1place is C-H stretching vibration peak in polymkeric substance; 1419cm
-1the C-H absorption peak at place is CH in PMG
2charateristic avsorption band.From above-mentioned analysis, synthetic polymkeric substance is the polyglycolic acid methyl esters.
Fig. 2 is the prepared polyglycolic acid methyl esters of embodiment 1
1the HNMR spectrogram, the known molecular structure from the polyglycolic acid methyl esters, its molecular structure is single,
1in the HNMR spectrogram, δ 11.5 is CF
3the solvent peak of COOD, δ 5.160 is (OCH
2cO) peak value on.
Figure 3 shows that the X-powder diffraction spectrum of polyglycolic acid methyl esters.As can be seen from the figure, the polyglycolic acid methyl esters is half crystal formation polymkeric substance, and 2 θ values are at 22.2 ° and 29.1 °.By swarming, calculate, degree of crystallinity is 63.33%.
The DSC curve of the polyglycolic acid methyl esters prepared shown in Fig. 4, be 36.4 ℃ by the glass transformation temperature of the visible the present embodiment product of curve, and Tc is 175.1 ℃, and fusing point is 219.7 ℃.
Fig. 5 can find out, at specific temperature, along with the increase of solid phase polycondensation time, limiting viscosity first increases afterwards and reduces in a scope, and the limiting viscosity of raw material is 0.1018dL/g as shown in the figure, and about solid-phase tack producing 120h, limiting viscosity reaches maximum value.In the increase along with the time, limiting viscosity starts to descend afterwards, and when the time increases to 200h, limiting viscosity drops to 0.4650dL/g.
Example 1
Get methyl glycolate 500g, add 0.4% Zinc diacetate dihydrate, add the polyfunctional reactant device of 1L, mix.Be warming up to 150 ℃, keep 1h, extract a large amount of methyl alcohol out, reach theoretical amount 95% left and right.Under 150 ℃, reaction system is vacuumized, vacuum tightness 600kPa, keep 1h; Under 160 ℃, vacuum tightness 300kPa, keep 1h; Under 170 ℃, vacuum tightness 100KPa, reaction 1h; Under 180 ℃, vacuum tightness 50KPa, reaction 2h.Under nitrogen protection, pulverize.Then under 180 ℃, vacuum tightness 70Pa, react 40h.Heat up 235 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.82%
Test data: limiting viscosity η
0=0.0998 δ Λ/γ; η
40 η=0.3310 δ Λ/γ
Weight-average molecular weight=30300
Tc=170.1 ℃
Fusing point=218.2 ℃
Glass transition temp=36.2 ℃
Degree of crystallinity=62.67%
Example 2
Get methyl glycolate 500g, add 0.4% two hydrated stannous chlorides, add the polyfunctional reactant device of 1L, mix.Be warming up to 150 ℃, keep 1h, extract a large amount of methyl alcohol out, reach theoretical amount 95% left and right.Under 150 ℃, reaction system is vacuumized, vacuum tightness 600kPa, keep 1h; Under 160 ℃, vacuum tightness 300kPa, keep 1h; Under 170 ℃, vacuum tightness 100KPa, reaction 1h; Under 180 ℃, vacuum tightness 50KPa, reaction 2h.Under nitrogen protection, pulverize.Under beat pulverizing latter 180 ℃, vacuum tightness 70Pa, reaction 40h.Heat up 235 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.87%
Test data: limiting viscosity η 0=0.1018 δ Λ/γ; η 40 η=0.3520 δ Λ/γ
Weight-average molecular weight=32200
Tc=175.1 ℃
Fusing point=219.7 ℃
Glass transition temp=36.4 ℃
Degree of crystallinity=63.33%
Example 3
Get methyl glycolate 500g, add 0.4% two hydrated stannous chlorides, add the polyfunctional reactant device of 1L, mix.Be warming up to 150 ℃, keep 1h, extract a large amount of methyl alcohol out, reach theoretical amount 95% left and right.Under 150 ℃, reaction system is vacuumized, vacuum tightness 100kPa, keep 1h; Under 160 ℃, vacuum tightness 50kPa, keep 1h; Under 170 ℃, vacuum tightness 10KPa, reaction 1h; Under 180 ℃, vacuum tightness 1KPa, reaction 2h.Under nitrogen protection, pulverize.Under beat pulverizing latter 180 ℃, vacuum tightness 70Pa, reaction 200h.Heat up 235 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.57%
Test data: limiting viscosity η 0=0.1018 δ Λ/γ; η 200 η=0.4650 δ Λ/γ
Weight-average molecular weight=40100
Tc=175.2 ℃
Fusing point=220.1 ℃
Glass transition temp=36.3 ℃
Degree of crystallinity=64.36%
Example 4
Get methyl glycolate 500g, add 0.1% two hydrated stannous chlorides, add the polyfunctional reactant device of 1L, mix.Be warming up to 80 ℃, keep 1h, wait to extract out a large amount of methyl alcohol, reach theoretical amount 95% left and right.Under 80 ℃, vacuumize, vacuum tightness 600kPa, keep 1h; Under 90 ℃, vacuum tightness 300kPa, keep 1h; Under 100 ℃, vacuum tightness 100KPa, reaction 1h; Under 100 ℃, vacuum tightness 50KPa, reaction 2h.Under nitrogen protection, pulverize.Under beat pulverizing latter 100 ℃, vacuum tightness 50KPa, reaction 10h.Heat up 235 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.57%
Test data: limiting viscosity η 0=0.1018 δ Λ/γ; η 10 η=0.2650 δ Λ/γ
Weight-average molecular weight=25100
Tc=170.2 ℃
Fusing point=218.1 ℃
Glass transition temp=36.1 ℃
Degree of crystallinity=62.36%
Example 5
Get methyl glycolate 500g, add 5% two hydrated stannous chlorides, add the polyfunctional reactant device of 1L, mix.Be warming up to 150 ℃, keep 1h, extract a large amount of methyl alcohol out, reach theoretical amount 95% left and right.Under 150 ℃, vacuumize, vacuum tightness 600kPa, keep 1h; Under 160 ℃, vacuum tightness 300kPa, keep 1h; Under 170 ℃, vacuum tightness 100KPa, reaction 1h; Under 180 ℃, vacuum tightness 50KPa, reaction 10h.Under nitrogen protection, pulverize.Under beat pulverizing latter 180 ℃, vacuum tightness 70Pa, reaction 300h.Heat up 235 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.57%
Test data: limiting viscosity η 0=0.2018 δ Λ/γ; η 300 η=0.3650 δ Λ/γ
Weight-average molecular weight=30100
Tc=176.2 ℃
Fusing point=221.1 ℃
Glass transition temp=36.3 ℃
Degree of crystallinity=68.36%
Example 6
Get methyl glycolate 500g, add 3% two hydrated stannous chlorides, add the polyfunctional reactant device of 1L, mix.Be warming up to 80 ℃, keep 1h, wait to extract out a large amount of methyl alcohol, reach theoretical amount 95% left and right.Under 80 ℃, vacuumize, vacuum tightness 100kPa, keep 1h; Under 90 ℃, vacuum tightness 50kPa, keep 1h; Under 100 ℃, vacuum tightness 10KPa, reaction 1h; Under 100 ℃, vacuum tightness 5KPa, reaction 2h.Under nitrogen protection, pulverize.Under beat pulverizing latter 100 ℃, vacuum tightness 10Pa, reaction 10h.Heat up 235 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.57%
Test data: limiting viscosity η 0=0.1018 δ Λ/γ; η 10 η=0.1650 δ Λ/γ
Weight-average molecular weight=18100
Tc=170.2 ℃
Fusing point=217.1 ℃
Glass transition temp=35.9 ℃
Degree of crystallinity=62.36%
Example 7
Get butyl glycolate 500g, add 0.5% two hydrated stannous chlorides, add the polyfunctional reactant device of 1L, mix.Be warming up to 180 ℃, keep 1h, extract a large amount of butanols out, reach theoretical amount 95% left and right.Start to vacuumize, under 180 ℃, vacuum tightness 500kPa, keep 1h; Under 185 ℃, vacuum tightness 250kPa, keep 1h; Under 185 ℃, vacuum tightness 100KPa, reaction 1h; Under 190 ℃, vacuum tightness 50KPa, reaction 2h.Under nitrogen protection, pulverize.Under beat pulverizing latter 190 ℃, vacuum tightness 70Pa, reaction 100h.Heat up 235 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.37%.The limiting viscosity η 0=0.1032 δ Λ/γ of resulting polymers; η 40 η=0.4450 δ Λ/γ, weight-average molecular weight is 39100.Example 8
Disubstituted-4-hydroxy methyl-butyrate 500g, add 1% Zinc diacetate dihydrate, adds the polyfunctional reactant device of 1L, mixes.Be warming up to 210 ℃, keep 1h, wait to extract out a large amount of methyl alcohol, reach theoretical amount 95% left and right.Start to vacuumize, under 210 ℃, vacuum tightness 300kPa, keep 1h; Under 220 ℃, vacuum tightness 100kPa, keep 1h; Under 230 ℃, vacuum tightness 100KPa, reaction 1h; Under 240 ℃, vacuum tightness 50KPa, reaction 2h.Under nitrogen protection, pulverize.Under beat pulverizing latter 250 ℃, vacuum tightness 70Pa, reaction 150h.Heat up 275 ℃, the melting discharging, cooling after, vacuum-drying 12h.The final product yield is 99.71%.Resulting polymers limiting viscosity η 0=0.1267 δ Λ/γ; η 40 η=0.5150 δ Λ/γ, weight-average molecular weight is 48200.
Claims (8)
1. a method for preparing the polyhydroxycarboxyliacid acid ester, described method comprises the following steps:
1) take Lewis acid as catalyzer, is 10-600KPa by hydroxycarboxylic acid esters monomer or hydroxy aliphatic acyl chlorides monomer at pressure, and polyreaction 1-10h under the condition that temperature is 80-230 ℃, obtain the polyhydroxycarboxyliacid acid ester oligomer; The 0.1-5.0% that described catalyst levels is hydroxycarboxylic acid esters monomer total mass;
2) the polyhydroxycarboxyliacid acid ester oligomer obtained under the protection of shielding gas, pulverising step 1);
3) by step 2) react 40-200h under the condition of oligopolymer solid phase polycondensation pressure 10Pa-100KPa, temperature 100-250 ℃ that obtains, obtain the polyhydroxycarboxyliacid acid ester;
Described hydroxycarboxylic acid esters monomer is methyl glycolate, ethyl glycollate, methyl lactate, ethyl lactate, butyl glycolate or 4 hydroxybutyric acid methyl esters, and hydroxy aliphatic acyl chlorides monomer is glycoloyl chlorine, lactic acid acyl chlorides;
The 0.1-1.0% that described catalyst levels is the hydroxycarboxylic acid esters total mass.
2. method according to claim 1, is characterized in that described catalyzer comprises: lime acetate, zinc acetate, two hydration zinc acetates, antimonous oxide, germanium dioxide, antimony trisulfide, tin protochloride, two hydrated stannous chlorides, stannous octoate, tin chloride, stannic oxide, chromic oxide, titanium dioxide, complexing Titanium series catalyst.
3. method according to claim 2, is characterized in that described catalyzer is a kind of in two hydration zinc acetates, antimonous oxide, two hydrated stannous chlorides, or two or more composite catalyst arbitrarily.
4. method according to claim 1, is characterized in that, step 1) is to carry out under the condition of temperature programming matching program step-down.
5. the polyhydroxycarboxyliacid acid ester prepared by method claimed in claim 1: it is characterized in that described polyhydroxycarboxyliacid acid ester has:
(a) 10,000～1, the weight-average molecular weight (Mw) in 000,000 scope,
(b) when for molecular weight distribution, weight-average molecular weight/number-average molecular weight (Mw/Mn) is than value representation, be 0.8～3.0,
(c) when the sheet material that compression moulding and crystallization obtain is measured, yellowness index (YI) is up to 50,
(d) at 250 ℃ of viscosity (η that measure after keeping 60 minutes
60) with the initial viscosity (η of mensuration after 250 ℃ of preheatings 5 minutes
0) ratio [(η
60/ η
0) * 100], the melt viscosity retention rate is greater than 35%.
6. polyhydroxycarboxyliacid acid ester according to claim 5: while it is characterized in that in nitrogen gas stream that described polyhydroxycarboxyliacid acid ester is 10ml/min at flow that heating rate with 2 ℃/min is from 50 ℃ of heating, temperature when its rate of weight loss in the time of 50 ℃ reaches 1% is 200 ℃ or higher.
7. polyhydroxycarboxyliacid acid ester according to claim 5: it is characterized in that the melt viscosity of described polyhydroxycarboxyliacid acid ester under the shearing rate of the temperature of 240 ℃ and 122/ second is 10～200,000Pas.
8. according to the described polyhydroxycarboxyliacid acid ester of claim 5-6 any one: it is characterized in that described polyhydroxycarboxyliacid acid ester is polyglycolic acid methyl esters, polyglycolic acid butyl ester, poly(lactic acid) methyl esters or poly-4 hydroxybutyric acid methyl esters.
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| CN107177032B (en) * | 2016-03-11 | 2019-04-02 | 上海浦景化工技术股份有限公司 | By the method for glycolic or methyl glycollate preparation high molecular weight polyglycolic acid |
| CN111647142B (en) * | 2019-09-17 | 2022-07-01 | 上海浦景化工技术股份有限公司 | Preparation method and system of polyhydroxycarboxylic acid ester or polyhydroxycarboxylic acid polymer |
| CN114428146A (en) * | 2022-01-27 | 2022-05-03 | 中国科学院宁波材料技术与工程研究所 | Method for analyzing molecular weight and distribution of polyhydroxyalkanoate by using gel permeation chromatography |
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| CN1332758A (en) * | 1999-09-10 | 2002-01-23 | 三井化学株式会社 | Polyurethane resin with degradability |
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| CN1332758A (en) * | 1999-09-10 | 2002-01-23 | 三井化学株式会社 | Polyurethane resin with degradability |
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