CN102516555A - Biodegradable branched aliphatic polyester multi-block copolymer and preparation method thereof - Google Patents
Biodegradable branched aliphatic polyester multi-block copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a biodegradable branched aliphatic polyester multi-block copolymer and a preparation method thereof. The biodegradable branched aliphatic polyester multi-block copolymer is provided by combining excellent biodegradability of aliphatic polyester and improved physical and mechanical properties of branched aliphatic polyester, the multi-block copolymer is a branched multi-block copolymer consisting of a chain segment I and a chain segment II, and the multi-block copolymer overcomes the defects about performance of the aliphatic polyester and has the advantages of high melt viscosity, high viscosity strength and the like.
Description
Technical field
The present invention relates to a kind of Biodegradable branched aliphatic polyester segmented copolymer and preparation method thereof.
Background technology
Biodegradable polymer is owing to its environmental friendliness and biomedical uses receive the extensive concern of academia and industry member, and its use can be alleviated " white pollution " problem that is caused by the traditional polymer material to a certain extent.Aliphatic polyester gets more and more people's extensive concerning as most important Biodegradable material, and it is mainly used in fields such as agricultural, packing, fiber and biological medicine.Poly-succinic fourth diester (PBS) is because its excellent comprehensive performance and excellent industrial application foreground become one of kind with fastest developing speed in the aliphatic polyester.Be considered to be hopeful most to realize one of industriallization and commercial Biodegradable Polymers at present.
Up to the present, aliphatic polyester particularly PBS is not also applied widely, except its price is higher than traditional polyolefine material far away, main also exists defective that very big relation is arranged with itself structure and performance.Compare with other aromatic polyester material; The obvious deficiency of aliphatic polyester is that its melt viscosity is low poor with melt strength; This mainly is because the polycondensation later stage, side reactions such as decarboxylation, cyclisation took place easily; Be difficult to obtain the high-molecular weight polyester, limited its application in film and foaming product field.Even can make film article, but because the influence of the molecular chain structure of polyester own, polyester film also exists transverse tensile strength low and shortcoming such as be prone to tear.This big limitations its in One-stop Shopping bag and mulch film Application for Field scope.For molecular weight that improves PBS and the transverse tensile strength that improves the PBS film article, PBS is carried out modification become the research focus of aliphatic polyester in recent years.People with a kind of with TiO
2And SiO
2The copolymerization mixed oxide be incorporated into (Seidel U, Eckert T, Chem.Fibers Int, 1999 in the aliphatic polyester reaction; 49,27), this catalyzer has high reactive behavior; Can shorten polymerization time, but there is the problem of form and aspect jaundice in the product of its preparation, thereby influences the outward appearance of product.In addition, on the transverse tensile strength that improves polyester film and this problem of easy tear strength, be the main difficult point of the ester modified existence of aliphatic poly always.
Branched polymer has different physics-chem characteristics.Drawing money on credit can improve the melt strength and the melt viscosity of polymkeric substance, and has the stress thickening effect, and this helps technology stability or the abscess homogeneity in preparation foam materials process of material in the blown film process.Short branching can improve the tearing toughness of film and improve its transparency.In the crystallinity aliphatic polyester, particularly in PBS, introduce melt strength and the melt viscosity that long-chain branch is expected to improve aliphatic polyester, introduce transverse tensile strength and tearing toughness that short-chain branch can also improve the aliphatic polyester film goods.In sum; The advantage of the improvement physical and mechanical properties that biological degradability that combining fat adoption ester is excellent and branching aliphatic polyester have can solve that aliphatic polyester exists that melt viscosity is low, there is the problem that transverse tensile strength is low and be prone to tear in melt strength difference and film article.
Summary of the invention
Goal of the invention
To deficiency of the prior art; The invention provides a kind of Biodegradable branched aliphatic polyester segmented copolymer, it can effectively overcome aliphatic polyester and have the problem that melt strength is poor, melt viscosity is low, the film article transverse tensile strength is low and be prone to tear.
Therefore, an object of the present invention is to provide a kind of Biodegradable branched aliphatic polyester segmented copolymer.
Another object of the present invention provides the preparation method of this Biodegradable branched aliphatic polyester segmented copolymer.
Technical scheme
To achieve these goals; The present invention provides a kind of Biodegradable branched aliphatic polyester segmented copolymer through combining fat adoption ester excellent biological degradability and the improved physical and mechanical properties of branching aliphatic polyester, and this segmented copolymer is the branching segmented copolymer that is made up of I segment and II segment.
Wherein, said I segment is hydroxy-end capped aliphatic poly ester oligomer or prepolymer, and it is by C
4-C
12Binary aliphatic acid mono and C
2-C
12The binary aliphatic alcohol monomer constitute, the 0.5-99.5% that it accounts for said branching segmented copolymer weight is preferably 15-85%, more preferably 30-70% most preferably is 40-60%.
Said II segment is hydroxy-end capped side chain aliphatic poly ester oligomer or prepolymer, and it is by C
4-C
6Binary aliphatic acid mono and C
2-C
22Binary aliphatic alcohol monomer and/or C
3-C
12Aliphatics trivalent alcohol monomer and/or C
8-C
22The glycerin fatty acid ester monomer constitutes, perhaps by the C that contains side chain
3-C
18Binary aliphatic acid mono and/or C
4-C
12Aliphatics triprotic acid monomer and C
4-C
6The binary aliphatic alcohol monomer constitute; Said II segment not necessarily is the condenses of epoxide, and the 0.5-99.5% that it accounts for said branching segmented copolymer weight is preferably 15-85%, and more preferably 30-70% most preferably is 40-60%.
Wherein, the weight percentage summation of I segment and II segment polyester prepolyer is 100%.
In technique scheme, C described in the I segment
4-C
12Aliphatic dibasic acid be selected from Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid and the arbitrary combination thereof; Said C
2-C
12Aliphatic dihydroxy alcohol be selected from terepthaloyl moietie, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, 1 is in 8-ethohexadiol and the arbitrary combination thereof.
In technique scheme, C described in the II segment
4-C
6Aliphatic dibasic acid be selected from Succinic Acid, pentanedioic acid, hexanodioic acid and the arbitrary combination thereof said C
2-C
22Aliphatic dihydroxy alcohol be selected from terepthaloyl moietie, 1,2-Ucar 35,1,2-butyleneglycol, 1,2-pentanediol, 1,2-pinakon, 1, contains the C of alkyl branches R at 2-ethohexadiol, 1,3 butylene glycol, 1,4 cyclohexane dimethanol
2-C
22In alkanediol and the arbitrary combination thereof, wherein the carbon number of R is 1～12, the said C that contains alkyl branches R
2-C
22Alkanediol is selected from the 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethylammonium-1; 5-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol, 2-butyl-2-ethyl-1; Ammediol, 2-ethyl-1,3-pinakon, 2-methyl isophthalic acid are in 8-ethohexadiol and the arbitrary combination thereof; Said C
3-C
12The aliphatics trivalent alcohol be selected from 1,2,4-trihydroxybutane, 1,2 is in 3-USP Kosher and the arbitrary combination thereof; And said C
8-C
22Glycerin fatty acid ester be selected from single caprylin, glyceryl monolaurate, glyceryl monostearate, Glycerin, mixed triester with caprylic acid capric acid and the arbitrary combination thereof.The said C that contains side chain
3-C
18Aliphatic dibasic acid be the C that contains alkyl branches R
3-C
18The chain docosandioic acid, wherein the carbon number of R is 1～12, the said C that contains alkyl branches R
3-C
18The chain docosandioic acid is selected from pyrovinic acid, methylglutaric acid, butyl suberic acid and the arbitrary combination thereof; Said C
4-C
12The aliphatics triprotic acid be selected from Hydrocerol A, the third three acid and the arbitrary combination thereof; Said C
4-C
6Aliphatic dihydroxy alcohol be selected from 1,4-butyleneglycol, 1,5-pentanediol, 1 is in 6-pinakon and the arbitrary combination thereof; And the condenses of said epoxide is optional in polyoxyethylene glycol, W 166, polytetramethylene glycol and arbitrary combination thereof.
In the preferred implementation of the present invention; Segmented copolymer of the present invention is selected from branching poly-succinic fourth diester-block-poly-succinic-1; 2-propylene glycol ester segmented copolymer, branching poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-be total to-Succinic Acid-1; The 2-pentanediol) ester segmented copolymer, branching poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-be total to-Succinic Acid-1; 2,4-trihydroxybutane) ester segmented copolymer, branching poly-succinic fourth diester-block-poly-succinic-1,2; 3-glycerine ester segmented copolymer, branching poly-succinic 1; 4-hexanaphthene dimethyl ester-block-gather (Succinic Acid terepthaloyl moietie-be total to-hexanodioic acid-1 the 2-ethohexadiol) ester segmented copolymer, branching poly-succinic fourth diester-block-polyoxyethylene glycol segmented copolymer, branching poly-succinic fourth diester-block-W 166 segmented copolymer, branching poly-succinic second diester-block-gather hexanodioic acid-1, in 2-Ucar 35 segmented copolymer and the arbitrary combination thereof.
Another aspect of the present invention provides a kind of preparation method of Biodegradable branched aliphatic polyester segmented copolymer, can be in following three kinds of methods any one:
Method 1
According to each the segmental part by weight described in the technique scheme; The mixture of the side chain aliphatic poly ester oligomer that aliphatic poly ester oligomer that said I segment is hydroxy-end capped or prepolymer and II segment are hydroxy-end capped or the condenses of prepolymer and/or epoxide joins in the reaction kettle; Then based on the gross weight of above-mentioned I segment and II segment polyester oligomer or prepolymer; The catalyzer that adds 0.01-1wt%; In temperature is 230-280 ℃, and vacuum tightness is to carry out constant temperature high vacuum reaction 30-400min under the condition of 0.1Pa-200Pa, thereby obtains segmented copolymer;
Method 2
According to each the segmental part by weight described in the technique scheme; The mixture of the side chain aliphatic poly ester oligomer that aliphatic poly ester oligomer that said I segment is hydroxy-end capped or prepolymer and II segment are hydroxy-end capped or the condenses of prepolymer and/or epoxide joins in the reaction kettle; In temperature is under 100-180 ℃; Gross weight based on above-mentioned I segment and II segment polyester oligomer or prepolymer; Add the chainextender of 0.5-4wt% and/or the catalyzer of 0.1-1wt% successively, under agitation react 30-120min, thereby obtain segmented copolymer; Perhaps
Method 3
According to each the segmental part by weight described in the technique scheme; The mixture of the side chain aliphatic poly ester oligomer that aliphatic poly ester oligomer that said I segment is hydroxy-end capped or prepolymer and II segment are hydroxy-end capped or the condenses of prepolymer and/or epoxide joins in the twin screw extruder; Setting extruder temperature is 90-180 ℃, and the residence time is 0.5-15min, based on the gross weight of above-mentioned I segment and II segment polyester oligomer or prepolymer; Add the chainextender of 1-5wt% and/or the catalyzer of 0.3-1wt% successively; After the shearing force that above-mentioned material process twin screw extruder provides,, thereby obtain segmented copolymer again through the water cooling slivering.
In the preparation method of Biodegradable branched aliphatic polyester segmented copolymer provided by the invention; Said I segment is that hydroxy-end capped aliphatic poly ester oligomer or prepolymer, II segment are the hydroxy-end capped side chain aliphatic poly ester oligomer or the condenses of prepolymer and/or epoxide, all can adopt the ordinary method preparation of this area.For example,
1. the aliphatic poly ester oligomer that said I segment is hydroxy-end capped or the preparation method of prepolymer can may further comprise the steps:
With mol ratio is 1: C (1.00-1.90)
4-C
12Binary aliphatic acid mono and C
2-C
12The binary aliphatic alcohol monomer join in the reaction kettle; Arrive 160-220 ℃ with temperature-programmed mode temperature reaction system; Under this temperature; Making above-mentioned monomer carry out esterification is more than the 95wt% of theoretical aquifer yield until aquifer yield, thereby obtains the hydroxy-end capped aliphatic poly ester oligomer of I segment; After esterification finishes; Based on the monomeric molar weight of above-mentioned aliphatic dibasic acid; In this reaction system, add the catalyzer of 0.01-0.6mol% and the stablizer of 0.003-0.1mol% successively; Stir 5-30min and guarantee that catalyzer evenly spreads in the system, and then to be 200-260 ℃ in temperature be to carry out polycondensation under the condition of 0.1Pa-1000Pa with vacuum tightness, thereby make the hydroxy-end capped aliphatic polyester prepolymer of I segment.
2. the side chain aliphatic poly ester oligomer that said II segment is hydroxy-end capped or the preparation method of prepolymer can may further comprise the steps:
With mol ratio is 1: C (1.00-2.00)
4-C
6Binary aliphatic acid mono and C
2-C
22Binary aliphatic alcohol monomer and or C
3-C
12Aliphatics trivalent alcohol monomer with or C
8-C
22The monomeric mixture of glycerin fatty acid ester is 1 with mol ratio perhaps: the C that contains side chain (1.00-2.00)
3-C
18Binary aliphatic acid mono and or C
4-C
12Aliphatics triprotic acid monomer and C
4-C
6The monomeric mixture of aliphatic dihydroxy alcohol; Join in the reaction kettle; Arrive 140-250 ℃ with temperature-programmed mode temperature reaction system; Under this temperature, make above-mentioned monomer carry out esterification and reach the 95wt% of theoretical aquifer yield, thereby obtain the hydroxy-end capped side chain aliphatic poly ester oligomer of II segment up to aquifer yield; After esterification finishes, based on above-mentioned C
4-C
6The binary aliphatic acid mono or contain the C of side chain
3-C
18The monomeric molar weight of aliphatic dibasic acid; The catalyzer that in this reaction system, adds 0.01-0.7mol%; Stir 5-30min and guarantee that catalyzer evenly spreads in the reaction system; And then to be 200-270 ℃ in temperature be to carry out polycondensation under the condition of 0.1Pa-1000Pa with vacuum tightness, thereby make the hydroxy-end capped side chain aliphatic polyester prepolymer of II segment.
Said II segment also can be the condenses of epoxide.
At aforesaid method 1; 2; 3; 1. used catalyzer can be selected from tetrabutyl titanate or 2.; Isopropyl titanate; Tetraethyl titanate; The coprecipitate of titanium oxide and silicon-dioxide; Antimony Trioxide: 99.5Min; Antimony acetate; Antimony glycol; Titanium ethylene glycolate; Aluminum isopropylate; Germanium dioxide; Germanium chloride; Zinc acetate; Burow Solution; Iron acetate; Cobaltous diacetate; Lanthanum acetate; The acetic acid zirconium; The acetic acid hafnium; Manganese acetate; Zinc chloride; Lanthanum trichloride; Zirconium chloride; Hafnium chloride; The methyl ethyl diketone lanthanum; The methyl ethyl diketone zirconium; The methyl ethyl diketone hafnium; Stannous octoate; Stannous oxalate; The vitriol oil; Glass putty; White tin oxide; Tin tetrachloride; C
2-C
22Alkyl titanium, C
2-C
22In titan-alkoxide, tosic acid, iron octoate, iron lactate, diethylamine, triethylamine, dimethyl-cetylamine and the arbitrary combination thereof.
Aforesaid method 1. or 2. used stablizer can be selected from phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, phosphorous acid diphenyl ester, ammonium phosphite or primary ammonium phosphate and the arbitrary combination thereof.
Used chainextender can be selected from the epoxies chainextender (as 4 in the aforesaid method 2 and 3; 5-epoxy hexane-1; 2-dicarboxylicacid 2-glycidyl ester, hexanaphthene-1,2-dicarboxylicacid 2-glycidyl ester, 4,5-oxo bridge hexanaphthene-1; 2-dioctyl phthalate didecyl ester, 4; 5-epoxy hexahydro--1,2-phthalic acid dihexyl, epoxy resin ly3505, BASF chainextender ADR-4380), the diisocyanates chainextender (like hexamethylene diisocyanate, diphenylmethanediisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond, isophorone diisocyanate, 4; 4-dicyclohexyl methyl hydride isocyanic ester), binary amides chainextender (like the two hexanolactams of hexanedioyl), binary acyl chloride chainextender (like the oxalic acid diacid chloride), anhydrides chainextender (like Succinic anhydried, terephthalic anhydride), 1; 3-phenyl-two (2-oxazoline), 1,4-phenyl-two (2-oxazoline), 2,2 '-two (2-oxazolines) and arbitrary combination thereof in.
Beneficial effect
The present invention provides a kind of Biodegradable branched aliphatic polyester segmented copolymer through the excellent biological degradability of combining fat adoption ester and the improved physical and mechanical properties of branching aliphatic polyester (like the transverse tensile strength and the tearing toughness of the melt strength that can improve polyester, melt viscosity, film article); This segmented copolymer is the branching segmented copolymer that is made up of I segment and II segment; Overcome the defective on the aliphatic polyester performance, had advantages such as melt viscosity height, melt strength height and excellent in stability.In addition, the existence of side chain can improve the aliphatic polyester film goods and have the shortcoming that is prone to tear, thereby has further expanded the Application Areas of biodegradable aliphatic polyester.
The preparation method of Biodegradable branched aliphatic polyester segmented copolymer provided by the invention has advantages such as technology is simple, production cost is low.
Embodiment
Provide embodiment below; But it is worthy of note that the present invention is not limited to these and implements example; The ordinary skill of this area to some nonessential change and adjustment that the present invention made, still belongs to protection scope of the present invention according to the content of foregoing invention.
Embodiment 1
Prepare Biodegradable branched poly-succinic fourth diester-block-poly-succinic-1,2-propylene glycol ester segmented copolymer may further comprise the steps:
1. synthesizing of hydroxy-end capped poly-succinic fourth two ester oligomers or prepolymer (I segment)
Be to take by weighing Succinic Acid and 1 at 1: 1.6 in molar ratio, 4-butyleneglycol 262g altogether joins in the reaction kettle, adds the Antimony Trioxide: 99.5Min (as catalyzer) of 0.02g then, and wherein, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (rotating speed 200r/min), reacting by heating system to 180 ℃ is warmed up to 220 ℃ with temperature-programmed mode then; Under this temperature, make above-mentioned monomer carry out esterification after aquifer yield arrives the 95wt% of theoretical aquifer yield, can obtain hydroxy-end capped poly-succinic fourth two ester oligomer 215g.Again temperature is raised to 230 ℃; Add the tetrabutyl titanate (as catalyzer) of 0.06g and the triphenyl phosphite (as stablizer) of 0.02g (is the 0.005mol% that accounts for Succinic Acid through calculating triphenyl phosphite); After stirring 15min, close the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (800r/min) fast of maintenance simultaneously; Isothermal reaction 180min under vacuum state promptly obtains hydroxy-end capped poly-succinic fourth diester prepolymer 190g.
2. hydroxy-end capped aliphatic poly Succinic Acid-1,2-propylene glycol ester oligopolymer or prepolymer (II segment) synthetic
Be to take by weighing Succinic Acid and 1 at 1: 2 in molar ratio; 2-Ucar 35 270g altogether joins in the reaction kettle; Add the tetrabutyl titanate of 0.01g and the Cobaltous diacetate of 0.01g (as catalyzer) then successively, wherein, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (150r/min), reacting by heating system to 160 ℃ is warmed up to 200 ℃ with temperature-programmed mode then; Under this temperature, make above-mentioned monomer carry out to obtain hydroxy-end capped poly-succinic-1,2-propylene glycol ester oligopolymer 220g after esterification reaches the 95wt% of theoretical aquifer yield until aquifer yield.Again temperature is raised to 230 ℃; Add antimony glycol 0.06g (as catalyzer); Close the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (600r/min) fast of maintenance simultaneously, isothermal reaction 300min under vacuum state; Promptly obtain hydroxy-end capped aliphatic poly Succinic Acid-1,2-propylene glycol ester prepolymer 192g.
3. Biodegradable branched poly-succinic fourth diester-block-poly-succinic-1, the preparation of 2-propylene glycol ester segmented copolymer
According to mass ratio is respectively to take by weighing the hydroxy-end capped poly-succinic-1 that 2. hydroxy-end capped poly-succinic fourth diester prepolymer that 1. above-mentioned steps obtain and above-mentioned steps obtain at 0.9: 0.1; 2-propylene glycol ester prepolymer 200g altogether joins in the reaction kettle; The Lanthanum trichloride (as catalyzer) that adds 0.04g tetrabutyl titanate and 0.01g then successively stirs 10min and guarantees that catalyzer is dispersed in (300r/min) in the reaction system.Stop logical nitrogen, be evacuated to below the 50Pa, and be rapidly heated, keep simultaneously stirring (1 fast to 260 ℃; 000r/min), isothermal reaction 150min under vacuum state promptly obtains Biodegradable branched poly-succinic fourth diester-block-poly-succinic-1,2-propylene glycol ester segmented copolymer 168g; Its number-average molecular weight is 76,000, and MWD is 2.8, and fusing point is 110 ℃; Percent crystallinity is 39%, and tensile strength is 40MPa, and elongation at break is 580%, and shock strength is 320J/m.
Embodiment 2
Prepare Biodegradable branched poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-altogether-Succinic Acid-1,2-pentanediol) ester segmented copolymer, may further comprise the steps:
1. synthesizing of hydroxy-end capped poly-succinic fourth two ester oligomers or prepolymer (I segment)
Be to take by weighing Succinic Acid and 1 at 1: 1.6 in molar ratio, 4-butyleneglycol 265g altogether joins in the reaction kettle, adds the Antimony Trioxide: 99.5Min (as catalyzer) of 0.06g then, and wherein, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (rotating speed 200r/min), reacting by heating system to 180 ℃ is warmed up to 220 ℃ with temperature-programmed mode then; Under this temperature, make above-mentioned monomer carry out esterification after aquifer yield arrives the 95wt% of theoretical aquifer yield, can obtain hydroxy-end capped poly-succinic fourth two ester oligomer 225g.Again temperature is raised to 230 ℃; Add titanium ethylene glycolate 0.05g (as catalyzer) and trimethyl phosphite 0.01g (as stablizer) simultaneously; After stirring 15min, close the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (800r/min) fast of maintenance simultaneously; Isothermal reaction 180min under vacuum state promptly obtains hydroxy-end capped poly-succinic fourth diester prepolymer 203g.
2. hydroxy-end capped side chain gathers the synthetic of (Succinic Acid butyleneglycol-be total to-Succinic Acid-1 the 2-pentanediol) ester oligomer or prepolymer (II segment)
Be in molar ratio take by weighing at 1: 2.0 Succinic Acid and aliphatic dihydroxy alcohol altogether 310g join in the reaction kettle; Wherein, Aliphatic dihydroxy alcohol is butyleneglycol and 1, the mixture of 2-pentanediol (1, the mol ratio of 2-pentanediol and butyleneglycol is 0.4: 0.6); Add the tetrabutyl titanate of 0.02g and the Cobaltous diacetate of 0.01g (as catalyzer) then successively, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (200r/min), reacting by heating system to 160 ℃ is warmed up to 210 ℃ with temperature-programmed mode then; Under this temperature, above-mentioned monomer is carried out after esterification reaches the 95wt% of theoretical aquifer yield until aquifer yield, can obtain hydroxy-end capped gathering (Succinic Acid butyleneglycol-altogether-Succinic Acid-1,2-pentanediol) ester oligomer 260g.Again temperature is raised to 240 ℃; Add antimony glycol 0.05g (as catalyzer) and trimethyl phosphite 0.01g (as stablizer) simultaneously; After stirring 15min, close the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (900r/min) fast of maintenance simultaneously; Isothermal reaction 300min promptly obtains hydroxy-end capped side chain and gathers (Succinic Acid butyleneglycol-altogether-Succinic Acid-1,2-pentanediol) ester prepolymer 215g under vacuum state.
The preparation of 3. Biodegradable branched poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-be total to-Succinic Acid-1 the 2-pentanediol) ester segmented copolymer
According to mass ratio is respectively to take by weighing the hydroxy-end capped side chain that 2. hydroxy-end capped poly-succinic fourth two ester oligomers that 1. above-mentioned steps obtain and above-mentioned steps obtain at 0.9: 0.1 to gather (Succinic Acid butyleneglycol-altogether-Succinic Acid-1; The 2-pentanediol) the common 200g of ester oligomer joins in the reaction kettle; The hafnium chloride (as catalyzer) that adds 0.04g tetrabutyl titanate and 0.01g then successively stirs 30min and guarantees that catalyzer is dispersed in (200r/min) in the reaction system.Stop logical nitrogen, be evacuated to below the 50Pa, and be rapidly heated to 260 ℃; Keep simultaneously stirring fast (900r/min), isothermal reaction 150min under vacuum state promptly obtains Biodegradable branched poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-altogether-Succinic Acid-1; The 2-pentanediol) ester segmented copolymer 172g, its number-average molecular weight is 83,000; MWD is 2.4, and fusing point is 111 ℃, and percent crystallinity is 41%; Tensile strength is 47MPa, and elongation at break is 390%, and shock strength is 180J/m.
Embodiment 3
Preparation branching poly-succinic fourth diester-block-gather (the Succinic Acid butyleneglycol-altogether-Succinic Acid-1,2, the 4-trihydroxybutane) the ester segmented copolymer, may further comprise the steps:
1. synthesizing of hydroxy-end capped poly-succinic fourth two ester oligomers or prepolymer (I segment)
Be to take by weighing Succinic Acid and 1 at 1: 1.6 in molar ratio, 4-butyleneglycol 265g altogether joins in the reaction kettle, adds the Antimony Trioxide: 99.5Min (as catalyzer) of 0.02g then, and wherein, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (rotating speed 200r/min), reacting by heating system to 180 ℃ is warmed up to 220 ℃ with temperature-programmed mode then; Under this temperature, make above-mentioned monomer carry out esterification after aquifer yield arrives the 95wt% of theoretical aquifer yield, can obtain hydroxy-end capped poly-succinic fourth two ester oligomer 213g.Again temperature is raised to 230 ℃; Add titanium ethylene glycolate 0.05g (as catalyzer) and triphenyl phosphite 0.01g (as stablizer) simultaneously; After stirring 15min, close the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (800r/min) fast of maintenance simultaneously; Isothermal reaction 180min under vacuum state promptly obtains hydroxy-end capped poly-succinic fourth diester prepolymer 190g.
2. hydroxy-end capped side chain gathers the synthetic of (Succinic Acid butyleneglycol-be total to-Succinic Acid-1,2 the 4-trihydroxybutane) ester oligomer or prepolymer (II segment)
Be in molar ratio take by weighing at 1: 1.4 Succinic Acid and aliphatic dihydroxy alcohol altogether 250g join in the reaction kettle, wherein, aliphatic dihydroxy alcohol is butyleneglycol and 1; 2; The mixture of 4-trihydroxybutane (butyleneglycol and 1,2, the mol ratio of 4-trihydroxybutane are 0.9: 0.1); Add the tetrabutyl titanate of 0.03g and the Burow Solution of 0.01g (as catalyzer) then successively, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (200r/min), reacting by heating system to 180 ℃ is warmed up to 230 ℃ with temperature-programmed mode then; Under this temperature, above-mentioned monomer is carried out after esterification reaches the 95wt% of theoretical aquifer yield until aquifer yield, can obtain hydroxy-end capped gathering (Succinic Acid butyleneglycol-altogether-Succinic Acid-1,2,4-trihydroxybutane) ester oligomer 204g.Again temperature is raised to 250 ℃, adds aluminum isopropylate 0.05g (as catalyzer) simultaneously, behind the stirring 15min; Close the channel of nitrogen valve and begin to be evacuated to below the 100Pa; Keep simultaneously stirring fast (900r/min), isothermal reaction 200min under vacuum state promptly obtains hydroxy-end capped side chain and gathers (Succinic Acid butyleneglycol-be total to-Succinic Acid-1; 2, the 4-trihydroxybutane) ester prepolymer 181g.
The preparation of 3. Biodegradable branched poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-be total to-Succinic Acid-1,2 the 4-trihydroxybutane) ester segmented copolymer
According to mass ratio is respectively to take by weighing hydroxy-end capped the gathering that 2. hydroxy-end capped poly-succinic fourth diester prepolymer that 1. above-mentioned steps obtain and above-mentioned steps obtain (Succinic Acid butyleneglycol-altogether-Succinic Acid-1 at 0.7: 0.3; 2; The 4-trihydroxybutane) the common 200g of ester prepolymer joins in the reaction kettle; The tin tetrachloride (as catalyzer) that adds 0.04g tetrabutyl titanate and 0.02g then successively stirs 20min and guarantees that catalyzer is dispersed in (200r/min) in the reaction system.Stop logical nitrogen, be evacuated to below the 100Pa, and be rapidly heated, keep simultaneously stirring fast (900r/min) to 260 ℃; Isothermal reaction 180min under vacuum state promptly obtains Biodegradable branched poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-altogether-Succinic Acid-1,2; The 4-trihydroxybutane) ester segmented copolymer 173g, its number-average molecular weight is 102,300; MWD is 2.9, and fusing point is 113 ℃, and percent crystallinity is 51%; Tensile strength is 53MPa, and elongation at break is 370%, and shock strength is 116J/m.
Embodiment 4
Prepare Biodegradable branched poly-succinic fourth diester-block-poly-succinic-1,2,3-glycerine ester segmented copolymer may further comprise the steps:
1. synthesizing of hydroxy-end capped poly-succinic fourth two ester oligomers or prepolymer (I segment)
Be to take by weighing Succinic Acid and 1 at 1: 1.6 in molar ratio, 4-butyleneglycol 265g altogether joins in the reaction kettle, adds the Antimony Trioxide: 99.5Min (as catalyzer) of 0.02g then, and wherein, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (rotating speed 200r/min), reacting by heating system to 180 ℃ is warmed up to 220 ℃ with temperature-programmed mode then; Under this temperature, make above-mentioned monomer carry out esterification after aquifer yield arrives the 95wt% of theoretical aquifer yield, can obtain hydroxy-end capped poly-succinic fourth two ester oligomer 210g.Again temperature is raised to 230 ℃; Add antimony acetate 0.06g (as catalyzer) and trimethyl phosphite 0.01g (as stablizer) simultaneously; After stirring 15min, close the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (800r/min) fast of maintenance simultaneously; Isothermal reaction 180min under vacuum state promptly obtains hydroxy-end capped poly-succinic fourth diester prepolymer 190g.
2. hydroxy-end capped side chain poly-succinic-1,2,3-glycerine ester oligopolymer or prepolymer (II segment) synthetic
Be to take by weighing Succinic Acid and 1 at 1: 1.3 in molar ratio; 2; 3-USP Kosher mixture 240g altogether joins in the reaction kettle; Add the tetrabutyl titanate of 0.02g and the manganese acetate of 0.01g (as catalyzer) then successively, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (200r/min), reacting by heating system to 160 ℃ is warmed up to 210 ℃ with temperature-programmed mode then; In this temperature, make above-mentioned monomer carry out obtaining hydroxy-end capped poly-succinic-1,2,3 glycerine ester oligopolymer 195g after esterification reaches the 95wt% of theoretical aquifer yield until aquifer yield.Again temperature is raised to 240 ℃, adds triethylamine 0.05g (as catalyzer) simultaneously, behind the stirring 15min; Close the channel of nitrogen valve and begin to be evacuated to below the 100Pa; Keep simultaneously stirring (900r/min) fast, isothermal reaction 100min under vacuum state promptly obtains hydroxy-end capped side chain poly-succinic-1; 2,3 glycerine ester oligopolymers or prepolymer 172g.
3. Biodegradable branched poly-succinic fourth diester-block-poly-succinic-1,2, the preparation of 3-glycerine ester segmented copolymer
According to mass ratio is respectively to take by weighing the hydroxy-end capped poly-succinic-1 that 2. hydroxy-end capped poly-succinic fourth two ester oligomers that 1. above-mentioned steps obtain and above-mentioned steps obtain at 0.8: 0.2; 2; 3-glycerine ester oligopolymer 200g altogether joins in the reaction kettle; The hafnium chloride (as catalyzer) that adds 0.01g tetrabutyl titanate and 0.01g then successively stirs 30min and guarantees that catalyzer is dispersed in (150r/min) in the reaction system.Stop logical nitrogen, be evacuated to below the 100Pa, and be rapidly heated, keep simultaneously stirring fast (1000r/min) to 270 ℃; Isothermal reaction 60min under vacuum state promptly obtains Biodegradable branched poly-succinic fourth diester-block-poly-succinic-1,2,3-glycerine ester segmented copolymer 182g; Its number-average molecular weight is 123,800, and MWD is 3.7, and fusing point is 105 ℃; Percent crystallinity is 47%, and tensile strength is 54MPa, and elongation at break is 290%, and shock strength is 110J/m.
Embodiment 5
Prepare biodegradable poly-succinic fourth diester-block-polyoxyethylene glycol segmented copolymer, may further comprise the steps:
Then according to mass ratio be respectively take by weighing at 9: 1 hydroxy-end capped poly-succinic fourth diester prepolymer that 1. step of embodiment 1 prepare and polyoxyethylene glycol (molecular weight 3000g/mol) altogether 150g join in the reaction kettle; The diethylamine (as catalyzer) that adds 0.05g then stirs 10min and guarantees that catalyzer is dispersed in (150r/min) in the reaction system.Stop logical nitrogen, be evacuated to below the 50Pa, and be rapidly heated, keep simultaneously stirring fast (1000r/min) to 260 ℃; Isothermal reaction 180min under vacuum state promptly obtains biodegradable poly-succinic fourth diester-block-polyoxyethylene glycol segmented copolymer 127g, and its number-average molecular weight is 78,200; MWD is 2.6, and fusing point is 114 ℃, and percent crystallinity is 41%; Tensile strength is 41MPa, and elongation at break is 627%, and shock strength is 310J/m.
Embodiment 6
Prepare biodegradable poly-succinic fourth diester-block-W 166 segmented copolymer, may further comprise the steps:
Then according to mass ratio be respectively take by weighing at 8: 2 hydroxy-end capped poly-succinic fourth diester prepolymer that 1. step of embodiment 1 prepare and W 166 (molecular weight 6000g/mol) altogether 150g join in the reaction kettle, add the hexamethylene diisocyanate (as chainextender) of 3g successively, reaction system is heated to 150 ℃; Stirring reaction 2h (800r/min) under the nitrogen protection promptly obtains biodegradable poly-succinic fourth diester-block-W 166 segmented copolymer 130g, and its number-average molecular weight is 135; 400, MWD is 2.7, and fusing point is 104 ℃; Percent crystallinity is 41%; Tensile strength is 39MPa, and elongation at break is 390%, and shock strength is 270J/m.
Embodiment 7
Prepare biodegradable poly-succinic second diester-block-gather hexanodioic acid-1,2-Ucar 35 segmented copolymer may further comprise the steps:
1. synthesizing of hydroxy-end capped poly-succinic second two ester oligomers or prepolymer (I segment)
Be in molar ratio take by weighing at 1: 1.4 Succinic Acid and terepthaloyl moietie altogether 620g join in the reaction kettle, add the Antimony Trioxide: 99.5Min (as catalyzer) of 0.10g then, wherein, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (rotating speed 200r/min), reacting by heating system to 180 ℃ is warmed up to 210 ℃ with temperature-programmed mode then; Under this temperature, make above-mentioned monomer carry out esterification after aquifer yield arrives the 95wt% of theoretical aquifer yield, can obtain hydroxy-end capped poly-succinic fourth two ester oligomer 510g.Again temperature is raised to 220 ℃; Add antimony acetate 0.15g (as catalyzer) and trimethyl phosphite 0.02g (as stablizer) simultaneously; After stirring 15min, close the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (800r/min) fast of maintenance simultaneously; Isothermal reaction 200min under vacuum state promptly obtains hydroxy-end capped poly-succinic second diester prepolymer 480g.
2. hydroxy-end capped side chain gathers hexanodioic acid-1,2-propylene glycol ester oligopolymer or prepolymer (II segment) synthetic
Be to take by weighing Succinic Acid and 1 at 1: 2 in molar ratio; 2-propylene glycol mixtures 300g altogether joins in the reaction kettle; Add the tetrabutyl titanate of 0.07g and the manganese acetate of 0.02g (as catalyzer) then successively, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (200r/min), reacting by heating system to 160 ℃ is warmed up to 210 ℃ with temperature-programmed mode then; In this temperature, above-mentioned monomer is carried out after esterification reaches the 95wt% of theoretical aquifer yield until aquifer yield, obtain hydroxy-end capped hexanodioic acid-1, the 2-Ucar 35 240g of gathering.Again temperature is raised to 240 ℃; Add triethylamine 0.05g (as catalyzer) simultaneously, behind the stirring 15min, close the channel of nitrogen valve and begin to be evacuated to below the 100Pa; Keep simultaneously stirring fast (900r/min); Isothermal reaction 100min under vacuum state promptly obtains hydroxy-end capped side chain and gathers hexanodioic acid-1,2-propylene glycol ester 210g.
3. Biodegradable branched poly-succinic second diester-block-gather hexanodioic acid-1, the preparation of 2-Ucar 35 segmented copolymer
According to mass ratio is the hydroxy-end capped hexanodioic acid-1 that gathers that respectively takes by weighing that 2. hydroxy-end capped poly-succinic second diester prepolymer that 1. above-mentioned steps obtain and above-mentioned steps obtain at 0.9: 0.1, and 2-propylene glycol ester prepolymer and chainextender HDI 500g altogether join in the twin screw extruder, sets 150 ℃ of the temperature of twin screw extruder; Screw speed 60r/min, the residence time is 10min, through twin screw extruder extrude, cooling, pelletizing; Can obtain Biodegradable branched poly-succinic second diester-block-gather hexanodioic acid-1,2-Ucar 35 segmented copolymer 380g, its number-average molecular weight is 101; 000, MWD is 1.9, and fusing point is 112 ℃; Percent crystallinity is 37%; Tensile strength is 39MPa, and elongation at break is 490%, and shock strength is 380J/m.
Comparing embodiment 1
Be in molar ratio take by weighing at 1: 1.6 Succinic Acid and butyleneglycol altogether 265g join in the reaction kettle; Add the tetrabutyl titanate of 0.04g and the Cobaltous diacetate of 0.01g (as catalyzer) then successively; Wherein, reaction kettle is equipped with high pure nitrogen interface, mechanical stirrer, water trap, prolong etc.Start stirring (150r/min), reacting by heating system to 160 ℃ is warmed up to 200 ℃ with temperature-programmed mode then; Under this temperature; Above-mentioned monomer is carried out after esterification reaches the 95wt% of theoretical aquifer yield until aquifer yield; Temperature is raised to 230 ℃, closes the channel of nitrogen valve and begin to be evacuated to below the 100Pa stirring (900r/min) fast of maintenance simultaneously; Isothermal reaction 120min under vacuum state promptly obtains hydroxy-end capped aliphatic poly Succinic Acid fourth diester prepolymer 196g; Join above-mentioned prepolymer in the reaction kettle then, add the Lanthanum trichloride (as catalyzer) of 0.05g tetrabutyl titanate and 0.01g, stir 10min and guarantee that catalyzer is dispersed in (300r/min) in the reaction system.Stop logical nitrogen, be evacuated to below the 50Pa, and be rapidly heated, keep simultaneously stirring (1 fast to 260 ℃; 000r/min), isothermal reaction 250min under vacuum state promptly obtains 170 homopolymer, and its number-average molecular weight is 38; 000, MWD is 2.9, and fusing point is 115 ℃, and percent crystallinity is 65%; Tensile strength is 31MPa, and elongation at break is 145%, and shock strength is 90J/m.
Claims (8)
1. Biodegradable branched aliphatic polyester segmented copolymer, this segmented copolymer is to be made up of I segment and II segment,
Wherein, said I segment is hydroxy-end capped aliphatic poly ester oligomer or prepolymer, and it is by C
4-C
12Binary aliphatic acid mono and C
2-C
12The binary aliphatic alcohol monomer constitute, it accounts for the 0.5-99.5% of said branching segmented copolymer weight;
Said II segment is hydroxy-end capped side chain aliphatic poly ester oligomer or prepolymer, and it is by C
4-C
6Binary aliphatic acid mono and C
2-C
22Binary aliphatic alcohol monomer and/or C
3-C
12Aliphatics trivalent alcohol monomer and/or C
8-C
22The glycerin fatty acid ester monomer constitutes, perhaps by the C that contains side chain
3-C
18Binary aliphatic acid mono and/or C
4-C
12Aliphatics triprotic acid monomer and C
4-C
6The binary aliphatic alcohol monomer constitute, said II segment not necessarily is the condenses of epoxide, it accounts for the 0.5-99.5% of said branching segmented copolymer weight;
Wherein, the weight percentage summation of I segment and II segment polyester prepolyer is 100%.
2. segmented copolymer according to claim 1, wherein, C described in the I segment
4-C
12Aliphatic dibasic acid be selected from Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid and the arbitrary combination thereof; Said C
2-C
12Aliphatic dihydroxy alcohol be selected from terepthaloyl moietie, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, 1 is in 8-ethohexadiol and the arbitrary combination thereof.
3. segmented copolymer according to claim 1, wherein, C described in the II segment
4-C
6Aliphatic dibasic acid be selected from Succinic Acid, pentanedioic acid, hexanodioic acid and the arbitrary combination thereof said C
2-C
22Aliphatic dihydroxy alcohol be selected from terepthaloyl moietie, 1,2-Ucar 35,1,2-butyleneglycol, 1,2-pentanediol, 1,2-pinakon, 1, contains the C of alkyl branches R at 2-ethohexadiol, 1,3 butylene glycol, 1,4 cyclohexane dimethanol
2-C
22In alkanediol and the arbitrary combination thereof, wherein the carbon number of R is 1～12, the said C that contains alkyl branches R
2-C
22Alkanediol is selected from the 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethylammonium-1; 5-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol, 2-butyl-2-ethyl-1; Ammediol, 2-ethyl-1,3-pinakon, 2-methyl isophthalic acid are in 8-ethohexadiol and the arbitrary combination thereof; Said C
3-C
12The aliphatics trivalent alcohol be selected from 1,2,4-trihydroxybutane, 1,2 is in 3-USP Kosher and the arbitrary combination thereof; And said C
8-C
22Glycerin fatty acid ester be selected from single caprylin, glyceryl monolaurate, glyceryl monostearate, Glycerin, mixed triester with caprylic acid capric acid and the arbitrary combination thereof; The said C that contains side chain
3-C
18Aliphatic dibasic acid be the C that contains alkyl branches R
3-C
18The chain docosandioic acid, wherein the carbon number of R is 1～12, the said C that contains alkyl branches R
3-C
18The chain docosandioic acid is selected from pyrovinic acid, methylglutaric acid, butyl suberic acid and the arbitrary combination thereof; Said C
4-C
12The aliphatics triprotic acid be selected from Hydrocerol A, the third three acid and the arbitrary combination thereof; Said C
4-C
6Aliphatic dihydroxy alcohol be selected from 1,4-butyleneglycol, 1,5-pentanediol, 1 is in 6-pinakon and the arbitrary combination thereof; And the condenses of said epoxide is selected from polyoxyethylene glycol, W 166, polytetramethylene glycol and the arbitrary combination thereof.
4. according to each described segmented copolymer among the claim 1-3; Wherein, Said segmented copolymer is selected from branching poly-succinic fourth diester-block-poly-succinic-1; 2-propylene glycol ester segmented copolymer, branching poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-be total to-Succinic Acid-1 the 2-pentanediol) ester segmented copolymer, branching poly-succinic fourth diester-block-gather (Succinic Acid butyleneglycol-be total to-Succinic Acid-1,2; The 4-trihydroxybutane) ester segmented copolymer, branching poly-succinic fourth diester-block-poly-succinic-1; 2,3-glycerine ester segmented copolymer, branching poly-succinic 1,4-hexanaphthene dimethyl ester-block-gather (Succinic Acid terepthaloyl moietie-altogether-hexanodioic acid-1; The 2-ethohexadiol) ester segmented copolymer, branching poly-succinic fourth diester-block-polyoxyethylene glycol segmented copolymer, branching poly-succinic fourth diester-block-W 166 segmented copolymer, branching poly-succinic second diester-block-gather hexanodioic acid-1, in 2-Ucar 35 segmented copolymer and the arbitrary combination thereof.
5. method for preparing the described Biodegradable branched aliphatic polyester segmented copolymer of claim 1 comprises in following three kinds of methods any one:
Method 1
According to described each the segmental part by weight of claim 1; The mixture of the side chain aliphatic poly ester oligomer that aliphatic poly ester oligomer that said I segment is hydroxy-end capped or prepolymer and II segment are hydroxy-end capped or the condenses of prepolymer and/or epoxide joins in the reaction kettle; Then based on the gross weight of above-mentioned I segment and II segment polyester oligomer or prepolymer; The catalyzer that adds 0.01-3wt%; In temperature is 230-280 ℃, and vacuum tightness is to carry out constant temperature high vacuum reaction 30-100min under the condition of 0.1Pa-200Pa, thereby obtains segmented copolymer;
Method 2
According to described each the segmental part by weight of claim 1; The mixture of the side chain aliphatic poly ester oligomer that aliphatic poly ester oligomer that said I segment is hydroxy-end capped or prepolymer and II segment are hydroxy-end capped or the condenses of prepolymer and/or epoxide joins in the reaction kettle; In temperature is under 100-180 ℃; Gross weight based on above-mentioned I segment and II segment polyester oligomer or prepolymer; Add chainextender and/or the 0.1-1wt% catalyzer of 0.5-4wt% successively, under agitation react 30-120min, thereby obtain segmented copolymer; Perhaps
Method 3
According to described each the segmental part by weight of claim 1; The mixture of the side chain aliphatic poly ester oligomer that aliphatic poly ester oligomer that said I segment is hydroxy-end capped or prepolymer and II segment are hydroxy-end capped or the condenses of prepolymer and/or epoxide joins in the twin screw extruder; Setting extruder temperature is 90-180 ℃, and the residence time is 0.5-15min, based on the gross weight of above-mentioned I segment and II segment polyester oligomer or prepolymer; Add the chainextender of 1-5wt% and/or the catalyzer of 0.3-1wt% successively; After the shearing force that above-mentioned material process twin screw extruder provides,, thereby obtain segmented copolymer again through the water cooling slivering.
6. preparation method according to claim 5; Wherein, said catalyzer is selected from coprecipitate, Antimony Trioxide: 99.5Min, antimony acetate, antimony glycol, titanium ethylene glycolate, aluminum isopropylate, germanium dioxide, germanium chloride, zinc acetate, Burow Solution, iron acetate, Cobaltous diacetate, lanthanum acetate, acetic acid zirconium, acetic acid hafnium, manganese acetate, zinc chloride, Lanthanum trichloride, zirconium chloride, hafnium chloride, methyl ethyl diketone lanthanum, methyl ethyl diketone zirconium, methyl ethyl diketone hafnium, stannous octoate, stannous oxalate, the vitriol oil, glass putty, White tin oxide, tin tetrachloride, the C of tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, titanium oxide and silicon-dioxide
2-C
22Alkyl titanium, C
2-C
22In titan-alkoxide, tosic acid, iron octoate, iron lactate, diethylamine, triethylamine, dimethyl-cetylamine and the arbitrary combination thereof.
7. preparation method according to claim 5, wherein, said chainextender is selected from epoxies chainextender, diisocyanates chainextender, binary amides chainextender, binary acyl chloride chainextender, anhydrides chainextender and the arbitrary combination thereof.
8. preparation method according to claim 7, wherein, said chainextender is selected from 4; 5-epoxy hexane-1,2-dicarboxylicacid 2-glycidyl ester, hexanaphthene-1,2-dicarboxylicacid 2-glycidyl ester, 4; 5-oxo bridge hexanaphthene-1,2-dioctyl phthalate didecyl ester, 4,5-epoxy hexahydro--1; 2-phthalic acid dihexyl, epoxy resin ly3505, BASF chainextender ADR-4380, hexamethylene diisocyanate, diphenylmethanediisocyanate, Toluene-2,4-diisocyanate; 4-vulcabond, isophorone diisocyanate, 4,4-dicyclohexyl methyl hydride isocyanic ester, the two hexanolactams of hexanedioyl, oxalic acid diacid chloride, Succinic anhydried, terephthalic anhydride, 1,3-phenyl-two (2-oxazoline), 1; In 4-phenyl-two (2-oxazoline), 2,2 '-two (2-oxazolines) and the arbitrary combination thereof.
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| CN105107015A (en) * | 2015-09-11 | 2015-12-02 | 江苏锦宇环境工程有限公司 | Preparation method of antibacterial healing-promoting biological foam dressing |
| CN108192105A (en) * | 2017-12-29 | 2018-06-22 | 王肖桦 | A kind of biology base Biodegradable multiblock polymer and its preparation method and application |
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| WO2024004987A1 (en) * | 2022-06-30 | 2024-01-04 | Dic株式会社 | Copolyester resin and method for producing same |
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