CN101054439A - High molecular weight degradation polymer and preparation method thereof - Google Patents
High molecular weight degradation polymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a macromolecule degradated polymer and its producing method belonging to material technical field. The polymer contains more than two monomers such as hydroxy acid or lactone or lactide formed by hydroxy acid, binary carboxylic acid or binary acid anhydride, aliphatic diamine or aromatic diamine, diatomic alcohol. The molecule chain of the polymer contains benzene ring. The molar ratio of the benzene ring monomer to polymer is 1-40%. The weight-average molecular weight of the polymer is more than 80000. The invention has the following process: adding the synthesis monomer material into the reaction vessel in proportion for a polymerization reaction, getting polyprotic oligomer with a certain polymeric level at 120-200 DEG C, with a vacuum degree of 10000Pa-100000Pa for 0.5-5 hours; polymerizing the polyprotic oligomer in vacuum with a vacuum degree of 1-50 Pa, at 150-300 DEG C for 10-50 hours in a catalytic environment, finally getting the target polymer. The invention can be widely used for fiber product, piece product, foaming product, injection molding product, membrane product and etc.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of in environment degradable material, described degradable material comprises multiple monomeric multipolymer.This degradable material excellent combination property can be widely used in fiber-like product, sheet material series products, foaming kind product, injection moulding series products, film product etc.
Background technology
From eighties of last century just, plastics develop into a kind of material that is widely used in every field gradually, and the consumption of plastics is compared with nineteen sixty, and whole world plastics consumption in 2000 has increased more than 100 times.Yet because the non-degradable of plastics, the ecosystem that uses and abandon us of the widespread use of plastics, particularly plastic wrap has caused serious threat; And conventional plastic burning generation great amount of carbon dioxide, cause serious Greenhouse effect; In addition, plastics are mainly derived from the petroleum-type Nonrenewable resources, and a large amount of uses of plastics certainly will cause the serious energy and human survival crisis.
According to expert statistics, land, whole world prospective oil has only about 5,000,000,000,000 tons at present, according to present oil production speed, can only use 30 or 40 years more at most.It is few that China belongs to prospective oil, but consume big country, and the China's Oil reserves account for global 1.7% (rank 11), but accounted for 7% (rank 2) yet consume; China's Oil 30% above dependence on import increased by 34.7% than import in 03 year in 04 year at present, and petroleum import amount from now on will further increase, and the China's Oil crisis is serious day by day.
Aspect environmental pollution, the plastics widespread use has caused serious " white pollution ", according to statistics, nineteen sixty, urban solid garbage was 390,000 tons, wherein plastic refuse only accounts for 1%, urban solid garbage was 24.7 hundred million tons in 2000, and plastic refuse has accounted for 10.7%, and annual now with the surprising quantity accumulation above 2,000 ten thousand tons.
Therefore, the reproducible degradative plastics of originating arises at the historic moment, and its importance is self-evident.
Biodegradable resin as versatility, compelling is aliphatic polyester, mainly contain poly(lactic acid) (PLA), polyhydroxy acid butyric ester (PHB), poly butylene succinate (PBS), polyethylene glycol succinate (PES), polycaprolactone (PCL) etc., wherein poly(lactic acid) is the more excellent typical case of prospect in the present degradation material.
In the above-mentioned aliphatic polyester, the fusing point of PLA near 170 ℃ because relatively poor relatively resistance toheat, in a lot of domain restrictions application.PBS and PES fusing point are near 100 ℃, and resistance toheat is relatively poor, and biodegradation rate is little, be short of intensity on the mechanical property.The flexibility excellence of PCL, but its fusing point has only about 60 ℃, so thermotolerance is low, its purposes is restricted, but biodegradation rate is very fast.
At the shortcoming of above-mentioned biodegradable resin material resistance toheat difference, there are many patents to relate to both at home and abroad and improve resistance toheat.With the poly(lactic acid) is example, improving aspect the poly(lactic acid) thermotolerance, patent CN1865321 relates to a kind of heat-proof polylactic acid copolymer and preparation method thereof, this multipolymer is that weight-average molecular weight is 20,000～600, L-poly(lactic acid)-D-polylactic-acid block copolymer of 000, wherein the weight ratio of L-poly(lactic acid) and D-poly(lactic acid) is 95: 5～5: 95, this segmented copolymer fusing point reaches more than 180 ℃.Yet the poly(lactic acid) fusing point of this patent preparation improves limited, still can not use at numerous areas.
Patent CN1793227 has introduced a kind of preparation method of thermal resistant easy processed polylactic resin.By in poly(lactic acid), introducing a kind of in thermotolerance material such as styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer or the polycarbonate, a kind of and oxidation inhibitor composition in the high melt speed macromolecular material aliphatic polyester (as polycaprolactone, poly butyric ester, poly butyric ester, poly butylene succinate etc.).Yet, introduced nondegradable styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer or polycarbonate in the poly(lactic acid), influenced the application of poly(lactic acid) as a kind of degradation material.
Patent CN 1217040C and EP1283285A2 have introduced a kind of acid fiber by polylactic, and its intensity under 90 ℃ reaches more than the 0.8cN/dtex, this fiber can bring into play than traditional acid fiber by polylactic superior the high-temperature mechanics characteristic of Duoing.Patent description has been by having added the aromatic polyester of 5～40wt% in polylactic resin, thereby increased substantially the resistance toheat of acid fiber by polylactic.This method by blend non-degradable aromatic polyester raising resistance toheat all has certain limitation at aspects such as consistency, degradation properties.
Except resistance toheat, single degradable resin also exists many deficiencies at aspects such as other physical and mechanical properties, processing characteristicies, haves much room for improvement.At present, many patents have related to the copolymerizing and blending modification of degradable resin.With the poly(lactic acid) is example, patent CN 1200972C provides a kind of lactic acid-base resin compositions, said composition comprises poly(lactic acid), aliphatic polyester and has polylactic acid chain segment and the mixture of aliphatic polyester segmental aliphatics blocked copolyester, has mainly improved the toughness and the processibility of single degradative resin poly(lactic acid) by blend.
Patent CN1215119C has introduced a kind of mixture of biodegradable polyesters, and it comprises: a kind of aromatic-aliphatic polyester (as " Ecoflex " of BASF AG), a kind of aliphatic polyester (as PBS), and poly(lactic acid).
Patent CN1785641 relates to a kind of production technique of comixed biodegradable material, and mixture comprises polycaprolactone, poly(lactic acid), plant amylum, zeolite powder, glycerol, vegetables oil.
Patent CN1858114 has introduced preparation and the product forming process that a kind of Biodegradable resin is compound and modification is resin dedicated, and it relates to PBS (poly-succinic acid-butanediol), PLA (poly(lactic acid)) biodegradable polymer polymkeric substance compound.Filling-modified through modified starch and activated inorganic filler obtains resin dedicated materials such as injection moulding, blowing, plastic uptake, hollow.
Patent CN1934191 provides a kind of thermoplastic resin composition, it is characterized in that the graft copolymer that comprises polymer in poly lactic acid series (A), contains the unitary acrylic acid polymer of methyl methacrylate monomer (B), rubber polymer graft polymerization vinyl monomer is obtained.
Patent CN1768115A relates to as the resin combination of the poly(lactic acid) of biology department's material and cellulose ester and moulding product thereof, also relate to a kind of moulding product that contain resin combination, described resin combination comprises poly(lactic acid) and is selected from cellulose ester, poly-(methyl) acrylate, second-order transition temperature is at least a in 60 ℃ or its above polyvinyl compound.
Patent CN1476459A relates to the manufacture method and the various uses of high-molecular aliphatic polyester multipolymer.Main by glycol, two acids material synthetic fat adoption esters, used linking agent to improve the molecular weight of polymkeric substance in the building-up process.And, by in aliphatic polyester copolymer, adding inorganic additives, can provide the shock-resistance excellence resin combination.
Summary of the invention
The object of the present invention is to provide a kind of high molecular degradable polymer and preparation method thereof.
The high molecular weight degradation polymer that the present invention proposes, contain two or more monomers in this polymkeric substance, monomer is: the lactone that alcohol acid or alcohol acid form or lactide, di-carboxylic acid or dibasic acid anhydride or dibasic ester, aliphatie diamine or aromatic diamine, dibasic alcohol, contain phenyl ring in the molecule segment of polymkeric substance, the molar ratio that phenyl ring class monomer accounts for polymkeric substance is 1～40%, the weight-average molecular weight of polymkeric substance is more than 80,000.
Among the present invention, contain phenyl ring in the molecule segment of polymkeric substance, the molar ratio that phenyl ring class monomer accounts for polymkeric substance is 5～30%.
Among the present invention, described alcohol acid be oxyacetic acid, lactic acid, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid or 6 hydroxycaproic acid one or more; The lactide that described alcohol acid forms is glycollide or rac-Lactide.
Among the present invention, described di-carboxylic acid be in oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, terephthalic acid or the m-phthalic acid one or more; Described dibasic acid anhydride is the acid anhydrides that is formed by oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, terephthalic acid or m-phthalic acid di-carboxylic acid; Dibasic ester is methyl esters or the ethyl ester that oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, terephthalic acid or m-phthalic acid di-carboxylic acid form.
Among the present invention, described aliphatie diamine be in quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine or the nonamethylene diamine one or more; Aromatic diamine be phenylenediamine, 3,3 '-two chloro-4,4 '-the poly-di-amine, 4,4 of ditan diamines, 3,3 '-two chloro-'-ditan diamines, benzidine or triazinediamine etc. in one or more.
Among the present invention, described dibasic alcohol be in ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol, butyleneglycol, pentanediol, hexylene glycol, nonanediol, undecane glycol, tridecane glycol, neopentyl glycol, hydroquinone two hydroxy ethyl ether or the Resorcinol dihydroxyethyl ether one or more.
A kind of preparation method of high molecular degradable polymer, concrete steps are as follows:
(1) the synthon raw material is joined by proportioning carries out polyreaction in the reactor, under inert gas atmosphere, under 120 ℃～200 ℃ temperature, reaction times is 0.5 hour～5 hours, and vacuum degree control is 10,000Pa～100,000Pa obtains the polynary oligopolymer of certain polymerization degree;
(2) with the polynary oligopolymer section of step (1) gained under vacuum environment, polymerization reaction take place under catalyst action, vacuum tightness is chosen to be 1～50Pa, temperature of reaction is 150～300 ℃, the reaction times is 10～50 hours, finally obtains required polymkeric substance;
The proportioning of raw material monomer is any of one of the following kind in the step (1): with [A] expression alcohol acid or the lactone of alcohol acid formation or the molar weight of lactide, molar weight with [B] expression di-carboxylic acid or dibasic acid anhydride or dibasic ester, molar weight with [C] expression aliphatie diamine or aromatic diamine, molar weight with [D] expression dibasic alcohol
The component of synthon is lactone or lactide A, di-carboxylic acid or dibasic acid anhydride or dibasic ester B and the dibasic alcohol D that alcohol acid or alcohol acid form, and then [A]/([A]+[B]+[D]) is 0.2～0.98, and [B]/([A]+[B]+[D]) is 0.01～0.4, [B]=[D];
Or the component of synthon is lactone or lactide A, di-carboxylic acid or dibasic acid anhydride or dibasic ester B, aliphatie diamine or aromatic diamine C and dibasic alcohol D that alcohol acid or alcohol acid form, D then, then [A]: ([A]+[B]+[C]+[D]) is (0.2～0.98): 1, [B]: ([A]+[B]+[C]+[D]) is (0.01～0.4): 1, [C]: ([A]+[B]+[C]+[D]) is (0.005～0.3): 1, and [B]: ([C]+[D]) is 1: 1;
Or the component of synthon is the lactone that forms of alcohol acid or alcohol acid or lactide A, di-carboxylic acid or dibasic acid anhydride or dibasic ester B, and aliphatie diamine or aromatic diamine C, then [A]: ([A]+[B]+[D]) is (0.2～0.98): 1, [B]: ([A]+[B]+[D]) is (0.01～0.4): 1, and [B]: [C] is 1: 1.
Among the present invention, in the step (1), polyreaction is to react in 1～5 normal atmosphere inert gas environment at pressure, perhaps reacts in the environment of normal pressure inert gas flow, perhaps reacts under the rough vacuum condition.
Among the present invention, in the step (1), add catalyzer in the polyreaction, catalyzer adopts tin compound (as tin dibromide, tindichloride, tin tetrabromide, tin tetrachloride, stannous octoate etc.), and the add-on of catalyzer is 0.001～1% of a monomer total amount.
In the present invention, the polymkeric substance resistance toheat that obtains is better.From the level inference of molecule segment, the interaction force between the molecular chain of single group aliphatic resin (as poly(lactic acid)) a little less than, more than second-order transition temperature, the chain displacement taking place relatively easily between the molecular chain, thereby has reduced the resistance toheat of polymkeric substance.The present invention is by introducing the phenyl ring class monomer of proportioning, rely on stronger interaction force between the phenyl ring, improved the power that influences each other between the molecule segment, make polymer molecular chain under comparatively high temps, still to be " fixed " well, be difficult for the chain displacement takes place, this is the major cause that polymkeric substance of the present invention can improve resistance toheat.On the other hand, benzene ring substance is difficult for adding too many, otherwise the degradation property of polymkeric substance is affected, in order to improve resistance toheat, the monomeric molar content of phenyl ring class should be greater than 5%, in order to make polymkeric substance to degrade, the monomeric molar content of phenyl ring class should be less than 40%, and more excellent content is 5～30%.
The polymer molecular chain that the present invention obtains can be by monomeric kind and add-on and then adjusting, thus the use properties of regulation and control polymkeric substance.Therefore, can solve the performance requriements of Application Areass such as fiber-like product, sheet material series products, foaming kind product, injection moulding class product product to degradation polymer.
The present invention can solve the shortcoming on existing degradable resin (as PLA, PCL, PBS, PBA, the PBAT etc.) performance well, thereby has widened the Application Areas of degradable material.
Excellent combination properties such as thermal characteristics of the present invention, physical and mechanical properties, biodegradability can be widely used in fiber-like product, sheet material series products, foaming kind product, injection moulding series products, film product etc.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
With 60 moles of rac-Lactides, 10 moles of terephthalic acids, 10 mole 1, the 4-butyleneglycol joins in the reactor, 190 ℃ of temperature of reaction, reaction 1.5 hours under the condition of the nitrogen gas stream protection of 5L/min; Then, add 0.1 mole tin dibromide in reaction system, be warming up to 220 ℃, vacuum is reaction 18 hours under the condition of 10Pa, obtains weight-average molecular weight and be 192,700 polymkeric substance, and the monomeric content of phenyl ring class is 12.5% in the polymkeric substance.
Embodiment 2
With 90 moles of rac-Lactides, 5 moles of terephthalic acids, 5 mole 1, the 4-butyleneglycol joins in the reactor, 190 ℃ of temperature of reaction, reaction 1.5 hours under the condition of the nitrogen gas stream protection of 5L/min; Then, add 0.125 mole tin dibromide in reaction system, be warming up to 220 ℃, vacuum is reaction 18 hours under the condition of 10Pa, obtains weight-average molecular weight and be 285,000 polymkeric substance, and the monomeric content of phenyl ring class is 5% in the polymkeric substance.
Embodiment 3
With 20 moles of rac-Lactides, 40 moles of terephthalic acids, 40 mole 1, the 4-butyleneglycol joins in the reactor, 190 ℃ of temperature of reaction, reaction 1.5 hours under the condition of the nitrogen gas stream protection of 5L/min; Then, add 0.125 mole tin dibromide in reaction system, be warming up to 220 ℃, vacuum is reaction 18 hours under the condition of 10Pa, obtains weight-average molecular weight and be 137,400 polymkeric substance, and the monomeric content of phenyl ring class is 40% in the polymkeric substance.
Embodiment 4
60 moles of rac-Lactides, 10 moles of terephthalic acids, 10 moles of hexanediamines are joined in the reactor 190 ℃ of temperature of reaction, reaction 1.5 hours under the condition of the nitrogen gas stream of 5L/min protection; Then, add 0.1 mole tin dibromide in reaction system, be warming up to 220 ℃, vacuum is reaction 18 hours under the condition of 10Pa, obtains weight-average molecular weight and be 268,000 polymkeric substance, and the monomeric content of phenyl ring class is 12.5% in the polymkeric substance.
Embodiment 5
98 moles of rac-Lactides, 1 mole of terephthalic acid, 1 mole of hexanediamine are joined in the reactor 190 ℃ of temperature of reaction, reaction 1.5 hours under the condition of the nitrogen gas stream of 5L/min protection; Then, add 0.125 mole tin dibromide in reaction system, be warming up to 220 ℃, vacuum is reaction 18 hours under the condition of 10Pa, obtains weight-average molecular weight and be 327,000 polymkeric substance, and the monomeric content of phenyl ring class is 1% in the polymkeric substance.
Embodiment 6
With 60 moles of rac-Lactides, 10 moles of terephthalic acids, 5 moles of hexanediamines, 5 mole 1, the 4-butyleneglycol joins in the reactor, 190 ℃ of temperature of reaction, reaction 1.5 hours under the condition of the nitrogen gas stream protection of 5L/min; Then, add 0.1 mole tin dibromide in reaction system, be warming up to 220 ℃, vacuum is reaction 18 hours under the condition of 10Pa, obtains weight-average molecular weight and be 216,000 polymkeric substance, and the monomeric content of phenyl ring class is 12.5% in the polymkeric substance.
Embodiment 7
With 80 moles of rac-Lactides, 10 moles of terephthalic acids, 3 moles of hexanediamines, 7 mole 1, the 4-butyleneglycol joins in the reactor, 190 ℃ of temperature of reaction, reaction 1.5 hours under the condition of the nitrogen gas stream protection of 5L/min; Then, add 0.125 mole tin dibromide in reaction system, be warming up to 220 ℃, vacuum is reaction 18 hours under the condition of 10Pa, obtains weight-average molecular weight and be 207,900 polymkeric substance, and the monomeric content of phenyl ring class is 10% in the polymkeric substance.
Embodiment 8
Use lactic acid to substitute rac-Lactide, the terephthalic acid methyl esters substitutes terephthalic acid, and other conditions obtain the polymkeric substance of weight-average molecular weight 160,000 at last with embodiment 1.At the catalyzer tosic acid of 0.01 mole of reaction fs adding, other condition is with embodiment 1, and the weight-average molecular weight of final product can reach 245,300.
Embodiment 9
Use lactic acid to substitute rac-Lactide, other condition is with embodiment 1, and the weight-average molecular weight of final product is 119,000.
At the catalyzer tosic acid of 0.01 mole of reaction fs adding, other condition is with embodiment 1, and the weight-average molecular weight of final product can reach 245,300.
Embodiment 10
Use triazinediamine to substitute hexanediamine, other condition is with embodiment 4, and the final product weight-average molecular weight can reach 327,900.
Embodiment 11
Use 4,4 '-ditan diamines replaces hexanediamine, and hexanodioic acid replaces terephthalic acid, and other condition is with embodiment 4, and the final product weight-average molecular weight can reach 175,000.
Embodiment 12
The category-A material is selected the miscellany of the caprolactone of 10 moles lactic acid, 10 moles glycollide and 40 moles for use, and other condition is with embodiment 1, and the product weight-average molecular weight that finally obtains is 183,000.
Embodiment 13
The comparative example 1, and monomer component and mole proportioning are constant, and the situation that obtains product under different technology conditions sees following table for details:
| Catalyzer | Catalyst content | Temperature (℃) | Time (h) | Vacuum tightness (Pa) | Weight-average molecular weight |
| Tin dibromide | 0.125％ | 220 | 18 | 50 | 163,000 |
| Tin dibromide | 0.125％ | 220 | 18 | 1 | 116,400 |
| Tin dibromide | 0.125％ | 220 | 10 | 10 | 158,000 |
| Tin dibromide | 0.125％ | 220 | 25 | 10 | 189,300 |
| Tindichloride | 0.125％ | 220 | 18 | 10 | 147,000 |
| Stannous octoate | 0.125％ | 220 | 18 | 10 | 149,200 |
| Tin dibromide | 0.125％ | 200 | 18 | 10 | 107,000 |
| Tin dibromide | 0.125％ | 240 | 18 | 10 | 166,000 |
| Tin dibromide | 0.2％ | 220 | 18 | 10 | 171,000 |
| Tin dibromide | 0.05％ | 220 | 18 | 10 | 148,700 |
Claims (9)
1, a kind of high molecular weight degradation polymer, it is characterized in that containing in this polymkeric substance two or more monomers, monomer is: the lactone that alcohol acid or alcohol acid form or lactide, di-carboxylic acid or dibasic acid anhydride or dibasic ester, aliphatie diamine or aromatic diamine, dibasic alcohol, contain phenyl ring in the molecule segment of polymkeric substance, the molar ratio that phenyl ring class monomer accounts for polymkeric substance is 1～40%, the weight-average molecular weight of polymkeric substance is more than 80,000.
2, high molecular weight degradation polymer according to claim 1 is characterized in that containing phenyl ring in the molecule segment of polymkeric substance, and the molar ratio that phenyl ring class monomer accounts for polymkeric substance is 5～30%.
3, high molecular weight degradation polymer according to claim 1, it is characterized in that described alcohol acid be oxyacetic acid, lactic acid, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid or 6 hydroxycaproic acid one or more; The lactide that described alcohol acid forms is glycollide or rac-Lactide.
4, high molecular weight degradation polymer according to claim 1, it is characterized in that described di-carboxylic acid be in oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, terephthalic acid or the m-phthalic acid one or more; Described dibasic acid anhydride is the acid anhydrides that is formed by oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, terephthalic acid or m-phthalic acid di-carboxylic acid; Dibasic ester is methyl esters or the ethyl ester that oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, terephthalic acid or m-phthalic acid di-carboxylic acid form.
5, high molecular weight degradation polymer according to claim 1, it is characterized in that aliphatie diamine be in quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine or the nonamethylene diamine one or more; Aromatic diamine is a phenylenediamine, 3,3 '-two chloro-4,4 '-ditan diamines, 3,3 '-two chloro-gather di-amine, 4, in 4 '-ditan diamines, benzidine or the triazinediamine one or more.
6, high molecular weight degradation polymer according to claim 1, it is characterized in that dibasic alcohol be in ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol, butyleneglycol, pentanediol, hexylene glycol, nonanediol, undecane glycol, tridecane glycol, neopentyl glycol, hydroquinone two hydroxy ethyl ether or the Resorcinol dihydroxyethyl ether one or more.
7, a kind of preparation method of high molecular degradable polymer as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) the synthon raw material is joined by proportioning carries out polyreaction in the reactor, under inert gas atmosphere, under 120 ℃～200 ℃ temperature, reaction times is 0.5 hour～5 hours, and vacuum degree control is 10,000Pa～100,000Pa obtains the polynary oligopolymer of certain polymerization degree;
(2) with the polynary oligopolymer section of step (1) gained under vacuum environment, polymerization reaction take place under catalyst action, vacuum tightness is chosen to be 1～50Pa, temperature of reaction is 150～300 ℃, the reaction times is 10～50 hours, finally obtains required polymkeric substance;
The proportioning of raw material monomer is any of one of the following kind in the step (1): with [A] expression alcohol acid or the lactone of alcohol acid formation or the molar weight of lactide, molar weight with [B] expression di-carboxylic acid or dibasic acid anhydride or dibasic ester, molar weight with [C] expression aliphatie diamine or aromatic diamine, molar weight with [D] expression dibasic alcohol
The component of synthon is lactone or lactide A, di-carboxylic acid or dibasic acid anhydride or dibasic ester B and the dibasic alcohol D that alcohol acid or alcohol acid form, and then [A]/([A]+[B]+[D]) is 0.2～0.98, and [B]/([A]+[B]+[D]) is 0.01～0.4, [B]=[D];
Or the component of synthon is lactone or lactide A, di-carboxylic acid or dibasic acid anhydride or dibasic ester B, aliphatie diamine or aromatic diamine C and dibasic alcohol D that alcohol acid or alcohol acid form, then [A]: ([A]+[B]+[C]+[D]) is (0.2～0.98): 1, [B]: ([A]+[B]+[C]+[D]) is (0.01～0.4): 1, [C]: ([A]+[B]+[C]+[D]) is (0.005～0.3): 1, and [B]: ([C]+[D]) is 1: 1;
Or the component of synthon is the lactone that forms of alcohol acid or alcohol acid or lactide A, di-carboxylic acid or dibasic acid anhydride or dibasic ester B, and aliphatie diamine [A]: ([A]+[B]+[D]) is (0.2～0.98): 1, [B]: ([A]+[B]+[D]) is (0.01～0.4): 1, and [B]: [C] is 1: 1.
8, the preparation method of high molecular degradable polymer according to claim 7, it is characterized in that in the step (1), polyreaction is to react in 1～5 normal atmosphere inert gas environment at pressure, perhaps reacts in the environment of normal pressure inert gas flow, perhaps reacts under the rough vacuum condition.
9, the preparation method of high molecular degradable polymer according to claim 7 is characterized in that adding catalyzer in the polyreaction in the step (1), and catalyzer is a tin compound, and the add-on of catalyzer is 0.001～1% of a monomer total amount.
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| CN101412804B (en) * | 2008-11-23 | 2011-01-19 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN102727355A (en) * | 2011-03-31 | 2012-10-17 | 美亚无纺布工业有限公司 | Lifting sling device |
| CN104725621A (en) * | 2015-03-20 | 2015-06-24 | 九洲生物技术（苏州）有限公司 | Polyester resin as well as preparation method and application |
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| CN104725621A (en) * | 2015-03-20 | 2015-06-24 | 九洲生物技术（苏州）有限公司 | Polyester resin as well as preparation method and application |
| CN104725621B (en) * | 2015-03-20 | 2016-10-05 | 九洲生物技术（苏州）有限公司 | A kind of polyester resin, its preparation method and application |
| WO2019095289A1 (en) * | 2017-11-17 | 2019-05-23 | 盐城天顺机械科技有限公司 | Polycondensation method for obtaining lactic acid, adipic acid and hexamethylenediamine terpolymer |
| WO2020087220A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Glycolide production with low solid residue |
| WO2020087216A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Polyglycolic acid copolymer composition and preparation thereof |
| WO2020087203A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Heat and aging resistant polyglycolide copolymer and composition thereof |
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| CN111171301A (en) * | 2020-02-12 | 2020-05-19 | 东华大学 | Preparation method and application of nitrogenous copolymerized polylactic acid |
| CN111171301B (en) * | 2020-02-12 | 2021-04-06 | 东华大学 | Preparation method and application of nitrogenous copolymerized polylactic acid |
| CN113150518A (en) * | 2021-04-14 | 2021-07-23 | 河北科技大学 | Full-biodegradable plastic alloy and preparation method thereof |
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