CN102796251B - Biodegradable polyester-polycarbonate multi-block copolymer and preparation method and application thereof - Google Patents

Abstract

The invention discloses biodegradable polyester-polycarbonate multi-block copolymer and a preparation method and application thereof. The biodegradable polyester-polycarbonate multi-block copolymer is AB block copolymer consisting of a chain segment A and a chain segment B, wherein the chain segment A is hydroxy-terminated polyester prepolymer; the chain segment B is hydroxy-terminated polycarbonate prepolymer; and the AB block copolymer has the number average molecular weight of 5,000 to 500,000 and the molecular weight distribution of 1 to 6. The block copolymer is low in production cost, the process is simple and is easy to operate, and an instrumental analysis and detection result is correct; and the copolymer has the tensile strength of 20 to 60MPa, the breaking elongation of 100 to 1,200 percent and the impact strength of more than 5KJ/m<2>, can be used as an environment-friendly polymer material, and an impact modifier of biodegradable polymer materials such as polybutylene succinate (PBS), polylactic acid and polyhydroxybutyric acid, and is high in application value.

Description

Biodegradable polyester-polycarbonate segmented copolymer and preparation method thereof and application

Technical field

The present invention relates to a kind of Biodegradable polyester-polycarbonate segmented copolymer and preparation method thereof and application.

Background technology

Day by day serious along with problem of environmental pollution, Biodegradable polymer material more and more causes people's attention.Wherein, aliphatic polyester is owing to having compared with low price with mechanical property and processing characteristics become the most economic biodegradable material preferably.

At present, the application of aliphatic polyester in high-end product field is limited is mainly that in its performance, existence is as low in melt strength, particularly because the structure of aliphatic polyester and polyolefine are as polyethylene and polyacrylic structural similitude, present height regularity, there is quite high degree of crystallinity and large spherocrystal, thereby caused its maximum defect---the restriction of fragility.As PBS, although have lower second-order transition temperature (42 ℃ of left and right), because degree of crystallinity is more than 40%, fragility is very high, and the shock strength of the PBS that weight-average molecular weight is 100,000 is only 46J/m.Therefore these shortcomings that, overcome biological aliphatic polyester have important scientific value and practice significance.

Copolymerization is polymer-modified a kind of common method.In order to improve the mechanical property of aliphatic polyester, the phenyl ring of introducing rigidity in polyester molecule chain is one of at present the most frequently used method, but exist serious transesterification reaction in its polymerization process, multipolymer is generally random copolymers, therefore the general decline of its fusing point is more.And due to the introducing of nondegradation phenyl ring, the degradation property degradation of aliphatic polyester.Polymer International 2,006 55, and 545 have reported that PBS and maleopimaric anhydride carry out the method that copolymerization carrys out modification PBS, and by copolymerization, the flexural strength of PBS and tensile strength have larger raising, not too obvious but shock strength improves.

The biodegradability that improves at present aliphatic polyester is mainly to introduce polyoxyethylene glycol in the molecular chain of polyester, and the polyether prepolymers such as polypropylene glycol are prepared segmented copolymer.Yet these class methods, although can improve the biodegradability of aliphatic polyester, improve its toughness, make its intensity decline to a great extent simultaneously.

Patent CN101649045 and CN102020772A have reported that soft section of aliphatic polyester introducing unbodied or vitreous state in a kind of crystalline aliphatic polyester molecular chain comes the crystalline aliphatic polyester of modification to prepare segmented copolymer, can obtain high performance biodegradable material.

Aliphatic polycarbonate has very strong application prospect because it has good physiologically acceptable performance, biodegradability and degradation production nonstaining property.The kindliness of aliphatic polycarbonate molecular chain is very good, and polymkeric substance has good toughness.Therefore, be expected to by the block copolymerization of aliphatic polyester and aliphatic polycarbonate, improve the performances such as the biocompatibility of aliphatic polyester and shock strength.

Summary of the invention

The object of this invention is to provide a kind of Biodegradable polyester-polycarbonate segmented copolymer and preparation method thereof and application.

Biodegradable polyester-polycarbonate segmented copolymer provided by the invention is the AB type segmented copolymer being comprised of A segment and B segment; Wherein, described A segment is hydroxy-end capped polyester prepolyer, and described B segment is hydroxy-end capped polycarbonate prepolymer; The number-average molecular weight of described A segment is 500-50,000, specifically can be 1,000-2, and 800,1,000-4,000,1,000-50,000 or 2,800-4,000, preferred 500-35,000, most preferably 1,000-20,000; The number-average molecular weight of described B segment is 500-50,000, specifically can be 2000-6300,500-2000,2000-50000,6300-50000,6300-18700 or 18700-50000, and preferably 1,000-35,000, most preferably 1,000-30,000; The mol ratio of described A segment and B segment is 10: 90-95: 5, specifically can be 1: 0.98-18.98,1: 1-8.03,1: 1.05-5.09,1: 4.98-5.06 or 1.8-9.08: 1, preferably 20: 80-95: 5.

The number-average molecular weight of described AB type segmented copolymer is 5,000～500,000, be specially 98100-10300,25600-500300,28500-102700,48500-438800,49200-97600,68500-89200,28500-129600,129600-368600 or 79400-98100, preferably 10,000-40,000, most preferably 20,000-30,000, molecular weight distribution is 1-6, specifically can be 1.5-5.9,1.6-4.5,1.9-3.9,2.2-2.9,1.9-3.6 or 2.6-5.9, preferably 1.2-4.5, most preferably 1.5-4; Fusing point is 92-110 ℃, specifically can be 95-113 ℃, 96-112 ℃, 103-111 ℃ or 105-109 ℃, tensile strength 20-59MPa, specifically can be 28-57MPa, 30-52MPa, 33-47MPa or 35-46MPa, 32MPa, elongation at break is 102-980%, specifically can be 410-900%, 500-870%, 530-770%, 570-730% or 610-700%, and shock strength is 5.1-41KJ/m ², specifically can be 7-35KJ/m ², 16-33KJ/m ², 18-32KJ/m ²or 22-31KJ/m ².

The method of the above-mentioned segmented copolymer of preparation provided by the invention, comprises the steps:

1) aliphatic dibasic acid that is 2-12 by the total number of carbon atoms and the total number of carbon atoms are that the aliphatic dihydroxy alcohol of 2-12 carries out esterification, carry out after completion of the reaction polycondensation, react the complete hydroxy-end capped polyester prepolyer that obtains;

2) aliphatic dihydroxy alcohol that is 2-12 by carbonic acid dibasic ester, the total number of carbon atoms and catalyst for ester exchange reaction mix and carry out transesterification reaction, carry out after completion of the reaction polycondensation, react the complete hydroxy-end capped polycarbonate prepolymer that obtains;

3) by step 1) hydroxy-end capped polyester prepolyer and the step 2 of gained) the hydroxy-end capped polycarbonate prepolymer of gained carries out chain extension copolyreaction under the effect of chainextender, reacts the complete described segmented copolymer that obtains.

In the method, described the total number of carbon atoms is that the aliphatic dibasic acid of 2-12 is selected from least one in oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, sebacic acid and dodecanedioic acid, preferably at least one in oxalic acid, succsinic acid and hexanodioic acid; Described the total number of carbon atoms is that the aliphatic dihydroxy alcohol of 2-12 is selected from ethylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, BDO, 1,5-pentanediol, 1, at least one in 6-hexylene glycol, decamethylene-glycol, 1,4 cyclohexane dimethanol, diethylene glycol and Triethylene glycol, preferred ethylene glycol, 1,4-butyleneglycol, 1, at least one in 6-hexylene glycol and 1,4 cyclohexane dimethanol;

Described carbonic acid dibasic ester is selected from least one in methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and diphenyl carbonate, preferably at least one in methylcarbonate, diethyl carbonate and diphenyl carbonate;

Described catalyst for ester exchange reaction is selected from the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, the total number of carbon atoms is the tin alkyl of 4-40, the total number of carbon atoms is the alkoxyl group tin of 4-40, the total number of carbon atoms is at least one in the alkyl germanium of 4-40 and alkoxyl group germanium that the total number of carbon atoms is 4-40, preferred glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, at least one in manganese acetate and stannous octoate, more preferably antimonous oxide, butyl (tetra) titanate, zinc acetate, salt of wormwood, at least one in manganese acetate and stannous octoate,

Described chainextender is selected from di-epoxy compounds, bisoxazoline, vulcabond, polycarbodiimide, two phthalic imidines, carboxylic acid anhydride, dicyclo imines ester, at least one in the two lactan of organosilazanes and diacyl, preferably hexanodioic acid two (3,4-epoxycyclohexyl methyl esters), N, N-diepoxy propyl benzamide, uracil, malonylurea, N-N-diepoxy propyl group imide, N-N-diepoxy propyl imidazole quinoline ketone, 2,2-two (2-bisoxazoline), tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), polymerization diphenylmethanediisocyanate, methylene-bis (4-cyclohexyl isocyanate), hexamethylene-diisocyanate (HDI), dicyclohexyl methyl hydride-4-4 '-vulcabond, 2,2,4-trimethyl cyclohexane vulcabond, two (phthalic imidines), 1,2,4,5-benzene tertacarbonic acid dianhydride, phthalic anhydride, succinyl oxide, Shuan bis-azolactone or bi-benzoxazine, octamethylcyclotetrasilazane, hexaphenyl three silazane, N, the two pyrrolidone of N '-phosphinylidyne, N, the two hexanolactams of N '-phosphinylidyne, N, the two laurolactams of N '-phosphinylidyne, N, the two pyrrolidone of N '-oxalyl, N, the two hexanolactams of N '-oxalyl, N, the two laurolactams of N '-oxalyl, N, the two pyrrolidone of N '-succinyl, N, the two pyrrolidone of N '-hexanedioyl, N, the two lactan of N '-hexanedioyl, N, the two pyrrolidone of N '-phthalyl, N, the two laurolactams of N '-phthalyl, N, the two tetramethyleneimine of N '-paraphenylene terephthalamide and N, at least one in the two laurolactams of N '-paraphenylene terephthalamide, preferably hexanodioic acid two (3,4-epoxycyclohexyl methyl esters), 2,2-two (2-bisoxazoline), tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene-diisocyanate, 1,2,4,5-benzene tertacarbonic acid dianhydride, phthalic anhydride, succinyl oxide, hexaphenyl three silazane and N, at least one in the two hexanolactams of N '-oxalyl.

Described step 1) in, described the total number of carbon atoms is that the aliphatic dihydroxy alcohol of 2-12 and the molar ratio of the aliphatic dibasic acid that the total number of carbon atoms is 2-12 are 3.0-1.0, specifically can be 1.0-2.1,1.6-3.0,1.6-2.1,1.0-1.6 or 2.1-3.0, preferred 2.0-1.0, more preferably 1.5-1.0; In described step of esterification, temperature is 100-300 ℃, is specially 150-250 ℃, 150-170 ℃ or 170-250 ℃, preferred 110-260 ℃, more preferably 150-230 ℃, the time is 2-20 hour, specifically can be 2-6 hour, 6-20 hour, 2-3 hour or 3-6 hour, preferably 3-15 hour; Described polycondensation is negative reaction, this reaction also needs to remove small molecules product in carrying out, to promote reaction to carry out, in this polycondensation steps, temperature is 150-300 ℃, be specially 180-280 ℃, 180-230 ℃, 180-240 ℃, 230-240 ℃, 230-280 ℃ or 240-280 ℃, preferably 150-280 ℃, more preferably 160-280 ℃, time is 1-20 hour, be specially 2-8 hour, 2-3 hour or 3-8 hour, preferred 1-10 hour, vacuum tightness is 1Pa～3 * 10 ⁴pa, specifically can be 1-1000Pa, 1-10Pa or 1000-30000Pa, preferably 1Pa～2 * 10 ⁴pa.

Described step 2) in, described the total number of carbon atoms is that the aliphatic dihydroxy alcohol of 2-12 and the molar ratio of described carbonic acid dibasic ester are 3.0-1.0, specifically can be 1.0-1.3,1.0-1.8,1.3-1.5,1.3-1.8 or 1.5-1.8, preferably 2.0-1.0, more preferably 1.5-1.0; In described transesterification steps, temperature is 70-280 ℃, be specially 160-210 ℃, 70-160 ℃, 70-210 ℃ or, preferred 80-230 ℃, more preferably 90-210 ℃, the time is 2-20 hour, preferably 3-15 hour; Described polycondensation is negative reaction, this reaction also needs to remove small molecules product in carrying out, to promote reaction, carry out, in this polycondensation steps, temperature is 150-280 ℃, specifically can be 150-180 ℃ or 180-280 ℃, preferred 150-250 ℃, more preferably 160-230 ℃, the time is 1-20 hour, vacuum tightness is 1Pa～3 * 10 ⁴pa, specifically can be 1-30Pa, 10-30Pa, 10-3 * 10 ⁴pa or 30-3 * 10 ⁴pa, preferably 1Pa～2 * 10 ⁴pa.

Described step 3), in, the ratio of the mole dosage sum that feeds intake of described chainextender and described hydroxy-end capped polyester prepolyer and described polycarbonate prepolymer is 0.3～6, specifically can be 0.6-6,0.85-4 or 1.1-3.3, preferably 0.5～4.

Described step 1) before described step of esterification, also add catalyst for esterification reaction, described catalyst for esterification reaction is selected from the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, the total number of carbon atoms is the tin alkyl of 4-40, the total number of carbon atoms is the alkoxyl group tin of 4-40, the total number of carbon atoms is at least one in the alkyl germanium of 4-40 and alkoxyl group germanium that the total number of carbon atoms is 4-40, preferred glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, at least one in manganese acetate and stannous octoate, more preferably antimonous oxide, butyl (tetra) titanate, zinc acetate, salt of wormwood, at least one in manganese acetate and stannous octoate,

The consumption of described catalyst for esterification reaction is that described the total number of carbon atoms is the 0-2% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, preferred 0-0.6%, and the consumption of described catalyst for esterification reaction is not 0; The consumption of described catalyst for ester exchange reaction is the 0-2% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, specifically can be 0-0.05%, 0.02-2%, 0.08-0.8%, 0.1-0.6% or 0.2-0.4%, preferably 0-0.6%;

Described step 1) after step of esterification before polycondensation steps, and described step 2) after transesterification steps before described polycondensation steps, all also can add polycondensation catalyst, described polycondensation catalyst is all selected from the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, the total number of carbon atoms is the tin alkyl of 4-40, the total number of carbon atoms is the alkoxyl group tin of 4-40, the total number of carbon atoms is the alkyl germanium of 4-40, the total number of carbon atoms is the alkoxyl group germanium of 4-40, the total number of carbon atoms is the zinc alkyl(s) of 4-40, the total number of carbon atoms is the alkoxyl group zinc of 4-40 and at least one in iron lactate, preferred glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, at least one in manganese acetate and stannous octoate, more preferably antimonous oxide, butyl (tetra) titanate, zinc acetate, salt of wormwood, at least one in manganese acetate and stannous octoate,

Described step 1) in, the consumption of polycondensation catalyst is that described the total number of carbon atoms is the 0-2% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, preferred 0-0.6%, the consumption of described polycondensation catalyst is not 0; Described step 2) in, the consumption of polycondensation catalyst is the 0-2% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, specifically can be 0-0.04%, 0.02-2.0%, 0.08-0.8%, 0.1-0.6% or 0.2-0.4%, preferred 0-0.6%, the consumption of described polycondensation catalyst is not 0;

Described step 2) step 3 afterwards), before chain extension copolyreaction step, also can add chain extending reaction catalyzer; Described chain extending reaction catalyzer is selected from least one in tertiary amines chemicals, mineral acid, metal, metal oxide, metal chloride, metal acetate salt, organic titanic compound, organic germanium compounds, organo-tin compound, organo-aluminium compound and organoiron compound, preferably at least one in triethylamine, dimethyl cetylamine, stannous octoate, tributyltin chloride, dibutyltin dilaurate, phosphonic acids calcium, lithium chloride, anhydrous zinc acetate, Zinc Undecylenate and zinc soap; The consumption of described chain extending reaction catalyzer is 0～5% of described hydroxy-end capped polyester prepolyer and described hydroxy-end capped polycarbonate prepolymer quality sum, specifically can be 0.001-5%, 0.04-0.6% or 0.1-0.3%, preferably 0～4%, more preferably 0～3%, the consumption of described chain extending reaction catalyzer is not 0;

Described step 3) described chain extending reaction is molten state chain extension, and reaction unit is reactor or twin screw extruder.In described reactor, carry out in described chain extending reaction step, temperature is 80-200 ℃, be specially 80-160 ℃, 80-135 ℃, 80-120 ℃, 120-200 ℃, 120-160 ℃, 120-135 ℃, 135-200 ℃, 135-160 ℃ or 160-200 ℃, preferably 90～190 ℃, time is 0.5-6 hour, specifically can be 0.5-4 hour, 0.5-3,3-4 or 4-6 hour, preferably 0.5-5 hour.

In described twin screw extruder, carry out in described chain extending reaction step, extruder temperature is 100-280 ℃, preferred 100-250 ℃, screw speed is 5-500r/min, be specially 20r/min, 80r/min or 300r/min, preferred 30-300r/min, the residence time is 0.5-30min, be specially 2min, 5min or 15min, preferably 2-15min.In described twin screw extruder, carry out in described chain extending reaction step, the temperature of ZhiIV district, screw rod I district and head is followed successively by: 100-220 ℃, 100-280 ℃, 100-280 ℃, 100-280 ℃ and 100-220 ℃, successively preferably 110-200 ℃, 120-200 ℃, 130-250 ℃, 130-200 ℃ and 100-200 ℃.The method specifically can be: hydroxy-end capped polyester prepolyer, polycarbonate prepolymer, chainextender and catalyzer are added to double-screw reactor by feeder and volume pump respectively, inlet amount is by regulating feeder and the frequency of volume pump to control material, material through react extrude after by the direct cooling slivering of water-bath, pelletizing.

The application of above-mentioned biodegradable polyester-polycarbonate segmented copolymer provided by the invention in preparing the impact modifier of biodegradated polymer materal, also belongs to protection scope of the present invention.

Biodegradable polyester-polycarbonate segmented copolymer production cost provided by the invention is low, simple process, and easy handling, instrumental analysis detected result is correct.The tensile strength of this multipolymer is 20～60MPa, and elongation at break is 100～1200%, and shock strength is greater than 5KJ/m ².The impact modifier that can be used as the biodegradated polymer materals such as environment friendly macromolecular material and PBS, poly(lactic acid) and polyhydroxybutyrate, has very high using value.

Accompanying drawing explanation

Fig. 1 is the hydroxy-end capped poly-succinic fourth diester prepolymer of embodiment 1 gained ¹h-NMR spectrogram;

Fig. 2 is the hydroxy-end capped poly-carbonic acid fourth diester prepolymer of embodiment 1 gained ¹h-NMR spectrogram;

Fig. 3 is the segmented copolymer containing poly-succinic fourth diester and poly-carbonic acid fourth diester of embodiment 1 gained ¹h-NMR spectrogram.

Embodiment

The chemical analysis method and the analytical instrument that in following embodiment, adopt are described as follows:

One, chemical structure and molecular weight and molecular weight distribution

The molecular weight of polyester prepolyer and the structure of segmented copolymer are all measured and are obtained by 400M nuclear magnetic resonance analyser (Bruker DMX-400), take deuterochloroform as solvent, and tetramethylsilane is interior mark.The molecular weight of segmented copolymer and molecular weight distribution are measured by gel chromatograph (GPC, Waters company).Have the polystyrene of Series Molecules amount of narrow molecular weight distributions as correcting standard specimen, trichloromethane is as drip washing phase, and measuring temperature is 40 ℃.

Two, thermal characteristics

The fusing point of polyester prepolyer and segmented copolymer is all measured and is obtained by differential scanning calorimetry (DSC), and scanning speed is 20 ℃/min.

Three, the test of stretching and impact property

The tensile strength of segmented copolymer and shock strength are measured and are obtained according to the testing standard of ASTM D638-97 and ASTM D256-97 respectively.

Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described reactant all can obtain from open commercial sources if no special instructions.

Embodiment 1, prepare biodegradable polyester-polycarbonate segmented copolymer

The method that this embodiment prepares biodegradable polyester-polycarbonate segmented copolymer comprises the steps:

1) prepare hydroxy-end capped polyester prepolyer

Under room temperature first by succsinic acid and BDO with mol ratio 1: 1.6 2500g altogether, join in the reactor of the 5L that High Purity Nitrogen replaced.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 150 ℃, and logical nitrogen gas stirring reaction, after 20 hours, rises to 230 ℃ by temperature, and pressure is slowly down to 10Pa, then polycondensation 8 hours.Obtain the wax-like oligopolymer of white, be the hydroxy-end capped poly-succinic fourth diester prepolymer (HO-PBS-OH) shown in formula I structural formula, the fusing point of this prepolymer is 108.2 ℃, Fig. 1 is its nucleus magnetic hydrogen spectrum figure and ownership thereof, according to the integral area of nucleus magnetic hydrogen spectrum, from following formula, can calculate its number-average molecular weight is 4,000.

$M_n=90+\frac{A_{\mathrm{\&delta;}=2.6}}{A_{\mathrm{\&delta;}=3.5-3.7}}\&times;172$

(formula I) HO-PBS-OH

2) prepare hydroxy-end capped polycarbonate prepolymer

Under room temperature first by BDO and methylcarbonate 1.8: 1 in molar ratio altogether the magnesium acetate of 2500g, 20g join successively in the reactor of the 5L that High Purity Nitrogen replaced.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 210 ℃, logical nitrogen gas stirring reaction is after 2 hours, temperature is risen to 280 ℃, the antimonous oxide that adds 5g, pressure is slowly down to 1Pa, polycondensation is 5 hours again, obtains oligopolymer, is the hydroxy-end capped poly-carbonic acid fourth diester prepolymer (HO-PBC-OH) shown in formula II structural formula.Fig. 2 is its nucleus magnetic hydrogen spectrum figure and ownership thereof, and according to the integral area of nucleus magnetic hydrogen spectrum, from following formula, can calculate its number-average molecular weight is 2000.

$M_n=90+\frac{A_{\mathrm{\&delta;}=4.1}}{A_{\mathrm{\&delta;}=3.5-3.7}}\&times;116$

(formula II) HO-PBC-OH

3) prepare biodegradable polyester-polycarbonate segmented copolymer

By above-mentioned steps 1) and step 2) prepolymer for preparing dry 3h at 100 ℃.By step 1) prepolymer 1 and the step 2 that obtain) prepolymer 2 (2500g altogether) that obtains and MDI be according in the reactor that joins successively the 5L that High Purity Nitrogen replaced of mol ratio 1: 1: 1.7 and 1.0g chain extending reaction octoate catalyst Asia tin.Above-mentioned reaction system is heated to 160 ℃, reaction 0.5h.Obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention (PBS-b-PBC), its structural formula is (n is that 22.7, m is 16.5) as shown in formula III, its number-average molecular weight is 10,300, molecular weight distribution is that 2.6, Fig. 3 is this multipolymer ¹h-NMR spectrogram.In molecular chain, the mol ratio of A segment and B segment is 1: 1, and this multipolymer fusing point is 111 ℃ (PBS segments), tensile strength 32MPa, and elongation at break 730%, shock strength is 30KJ/m ².

(formula III) PBS-b-PBC

Embodiment 2, prepare biodegradable polyester-polycarbonate segmented copolymer

1) prepare hydroxy-end capped polyester prepolyer

Under room temperature, first by sebacic acid and BDO, with mol ratio 1: 3,2500g, 0.5g butyl (tetra) titanate joined in the reactor of the 5L that High Purity Nitrogen replaced altogether.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 300 ℃, and logical nitrogen gas stirring reaction, after 2 hours, adds butyl (tetra) titanate 50g, and pressure is slowly down to 1Pa, then polycondensation 1 hour.Obtain the wax-like oligopolymer of white, its fusing point is 73 ℃, and number-average molecular weight is 1,000.

2) prepare hydroxy-end capped polycarbonate prepolymer

Under room temperature first by ethylene glycol and diethyl carbonate 1: 1 in molar ratio altogether the salt of wormwood of 2500g, 0.05g join successively in the reactor of the 5L that High Purity Nitrogen replaced.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 70 ℃, and logical nitrogen gas stirring reaction, after 20 hours, rises to 150 ℃ by temperature, and pressure is slowly down to 3 * 10 ⁴pa, then polycondensation 1 hour.Obtain polycarbonate oligomer, its fusing point is 58 ℃, and number-average molecular weight is 500.

3) prepare biodegradable polyester-polycarbonate segmented copolymer

By step 1) and step 2) prepolymer for preparing dry 3h at 100 ℃.By this by step 1) prepolymer 1, the step 2 that obtain) prepolymer 2 that obtains and MDI join in the reactor of the 5L that High Purity Nitrogen replaced successively according to 8: 1: 2.7 (wherein two prepolymer quality amount to 2500g) of mol ratio.Above-mentioned reaction system is heated to 80 ℃, reaction 6h, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is 5,000, molecular weight distribution is 6.0, in molecular chain, the mol ratio of A segment and B segment is 8.03: 1, and fusing point is 95 ℃ (PBS segments), tensile strength 20MPa, elongation at break 102%, shock strength is 5.1KJ/m ².

Embodiment 3, prepare biodegradable polyester-polycarbonate segmented copolymer

By embodiment 2 steps 1) and step 2) prepolymer for preparing dry 3h at 100 ℃.This polyester prepolyer, polycarbonate prepolymer, HDI are joined in the reactor of the 5L that High Purity Nitrogen replaced successively according to 19: 1: 120 (wherein two prepolymer quality amount to 2000g) of mol ratio and the sub-tin of 100g chain extending reaction octoate catalyst.Above-mentioned reaction system is heated to 200 ℃, reaction 3h, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is 25,600, molecular weight distribution is 2.2, in molecular chain, the mol ratio of A segment and B segment is 18.98: 1, and fusing point is 113 ℃ (PBS segments), tensile strength 36MPa, elongation at break 660%, sample punching constantly.

Embodiment 4, prepare biodegradable polyester-polycarbonate segmented copolymer

By the step 1 of the embodiment of the present invention 1) and step 2) prepolymer for preparing dry 3h at 100 ℃.This polyester prepolyer, polycarbonate prepolymer, HDI are joined in the reactor of the 5L that High Purity Nitrogen replaced successively according to mol ratio 1: 9: 10 (wherein two prepolymer quality amount to 1000g), 3g chain extending reaction catalyst of triethylamine.Above-mentioned reaction system is heated to 200 ℃; under nitrogen protection, stirring reaction 1.5h obtains Biodegradable polyester-polycarbonate block copolymer provided by the invention; its number-average molecular weight is for being 98; 100, molecular weight distribution is 1.9, and in molecular chain, the mol ratio of A segment and B segment is 1.02: 9; fusing point is 103 ℃ (PBS segments); tensile strength 30MPa, elongation at break 530%, shock strength is 31KJ/m ².

Embodiment 5, prepare biodegradable polyester-polycarbonate segmented copolymer

The method that this embodiment prepares biodegradable polyester-polycarbonate segmented copolymer comprises the steps:

1) prepare hydroxy-end capped polyester prepolyer

Under room temperature first by succsinic acid and BDO 1: 1 in molar ratio altogether the tosic acid of 2500g, 50g join successively in the reactor of the 5L that High Purity Nitrogen replaced.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 100 ℃, and logical nitrogen gas stirring reaction, after 3 hours, adds stannous octoate 0.5g, and temperature is risen to 150 ℃, and pressure is slowly down to 1,000Pa, then polycondensation 20 hours.Obtain the wax-like oligopolymer of white, its fusing point is 108 ℃, and its number-average molecular weight is 50,000.

2) prepare hydroxy-end capped polycarbonate prepolymer

Under room temperature first by 1,6-hexylene glycol and methylcarbonate 3: 1 in molar ratio altogether the butyl (tetra) titanate of 2500g, 15g (for titan-alkoxide) join successively in the reactor of the 5L that High Purity Nitrogen replaced.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 160 ℃, and logical nitrogen gas stirring reaction, after 3 hours, rises to after 180 ℃ until temperature, and pressure is slowly down to 30Pa, then polycondensation 20 hours.Obtain polycarbonate oligomer, its fusing point is 59 ℃, and its number-average molecular weight is 50,000.

3) prepare biodegradable polyester-polycarbonate segmented copolymer

By step 1) and step 2) prepolymer for preparing dry 3h at 100 ℃.This polyester prepolyer, polycarbonate prepolymer, HDI were joined in the reactor of the 5L that High Purity Nitrogen replaced successively according to 8: 1: 13 (wherein two prepolymer quality amount to 1000g) of mol ratio.Above-mentioned reaction system is heated to 120 ℃; stirring reaction 6h under nitrogen protection; obtain Biodegradable polyester-polycarbonate block copolymer provided by the invention, number-average molecular weight is 438,800; molecular weight distribution is 3.6; in molecular chain, the mol ratio of A segment and B segment is 8.02: 1, and fusing point is 103 ℃ (PBS segments), tensile strength 33MPa; elongation at break 700%, shock strength is 33KJ/m ².

Embodiment 6, prepare biodegradable polyester-polycarbonate segmented copolymer

1) prepare hydroxy-end capped polyester prepolyer

Under room temperature first by succsinic acid and BDO with mol ratio 1: 2.1 2500g altogether, the manganese acetate of 5g joins in the reactor of the 5L that High Purity Nitrogen replaced.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 170 ℃, and logical nitrogen gas stirring reaction, after 6 hours, rises to 240 ℃ by temperature, adds the glass putty of 30g, and pressure is slowly down to 3 * 10 ⁴pa, then polycondensation 3 hours.Obtain the wax-like oligopolymer of white, its fusing point is 116 ℃, and number-average molecular weight is 2,800.

2) prepare hydroxy-end capped polycarbonate prepolymer

Under room temperature first by BDO and diethyl carbonate 1.5: 1 in molar ratio altogether the magnesium acetate of 2500g, 2.5g join successively in the reactor of the 5L that High Purity Nitrogen replaced.Simultaneous reactions still equipment High Purity Nitrogen inlet mouth, mechanical stirrer, prolong.Above-mentioned reaction system is controlled to 280 ℃, and logical nitrogen gas stirring reaction, after 5 hours, rises to 180 ℃ by temperature, adds the antimonous oxide of 0.025g, and pressure is slowly down to 10Pa, then polycondensation 20 hours.Obtain polycarbonate oligomer, its fusing point is 68 ℃, and number-average molecular weight is 6,300.

3) prepare biodegradable polyester-polycarbonate segmented copolymer

By above-mentioned steps 1) and step 2) prepolymer for preparing dry 3h at 100 ℃.This pet copolyester prepolymer, polycarbonate prepolymer, HDI are joined in the reactor of the 5L that High Purity Nitrogen replaced successively according to 1: 5: 24 (wherein two prepolymer quality amount to 1000g) of mol ratio, 0.01g chain extending reaction catalyzer dibutyltin dilaurate.Above-mentioned reaction system is heated to 160 ℃; stirring reaction 3h under nitrogen protection; obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is for being 48,500; molecular weight distribution is 1.0; in molecular chain, the mol ratio of A segment and B segment is 1: 5.05, and fusing point is 109 ℃ (PBS segments), tensile strength 38MPa; elongation at break 980%, shock strength is 35KJ/m ².

Embodiment 7, prepare biodegradable polyester-polycarbonate segmented copolymer

Adopt and the identical prepolymer of embodiment 6 and chain extension condition, only by HDI, change chainextender into succinyl oxide, chain extending reaction catalyzer changes triethylamine into by dibutyltin dilaurate, the consumption of this chain extending reaction catalyzer is 3g, after completion of the reaction, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is 28, 500, molecular weight distribution is 3.9, in molecular chain, the mol ratio of A segment and B segment is 1: 4.98, fusing point is 112 ℃ of (PBS segment) tensile strength 35MPa, elongation at break 770%, sample punching constantly.

Embodiment 8, prepare biodegradable polyester-polycarbonate segmented copolymer

In this embodiment, polyester prepolyer used is by the step 1 of embodiment 4) prepare, polycarbonate prepolymer used is prepared as follows:

Under room temperature, first by 1,5-PD and diphenyl carbonate 3: 1 in molar ratio 2500g, tosic acid 10g altogether, join successively in the reactor of the 5L that High Purity Nitrogen replaced.The other the same as in Example 3, obtains polycarbonate oligomer, and its fusing point is 63 ℃, and number-average molecular weight is 500.

By the step 1 of embodiment 4) polyester prepolyer for preparing and above-mentioned polycarbonate prepolymer be according to reacting with the identical preparation condition of the embodiment of the present invention 1, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, number-average molecular weight is 89,200, molecular weight distribution is 4.5, in molecular chain, the mol ratio of A segment and B segment is 1.05: 1, fusing point is 92 ℃ (PBS segments), tensile strength is 28MPa, elongation at break 980%, shock strength is 41KJ/m ².

Embodiment 9, prepare biodegradable polyester-polycarbonate segmented copolymer

In this embodiment, polyester prepolyer used is by the step 1 of embodiment 4) prepare, polycarbonate prepolymer used is prepared as follows:

Under room temperature first by hexylene glycol and diphenyl carbonate 2.5: 1 in molar ratio altogether 2500g join successively in the reactor of the 5L that High Purity Nitrogen replaced.The other the same as in Example 4.Obtain polycarbonate oligomer, its fusing point is 53 ℃, and number-average molecular weight is 18,700.

By the step 1 of embodiment 4) polyester prepolyer for preparing and above-mentioned polycarbonate prepolymer be according to reacting with the identical preparation condition of the embodiment of the present invention 1, obtain Biodegradable polyester-polycarbonate block copolymer provided by the invention, number-average molecular weight is 102,700, molecular weight distribution is 5.9, and in molecular chain, the mol ratio of A segment and B segment is 0.98: 1, fusing point is 106 ℃, tensile strength is 36MPa, and elongation at break is 500%, and shock strength is 16KJ/m ².

Embodiment 10, prepare biodegradable polyester-polycarbonate segmented copolymer

In this embodiment, polyester prepolyer used is by the step 1 of embodiment 1) prepare, polycarbonate prepolymer used is prepared by embodiment 8, by above-mentioned two prepolymers dry 3h at 100 ℃.By above-mentioned polyester prepolyer, polycarbonate prepolymer, HDI, according to mol ratio 9: 5: 16,1000g, the sub-tin of 50g chain extending reaction octoate catalyst joined in the reactor of the 5L that High Purity Nitrogen replaced successively altogether.Above-mentioned reaction system is heated to 135 ℃; under nitrogen protection, stirring reaction 4h obtains segmented copolymer; its number-average molecular weight is for being 500; 300, molecular weight distribution is 1.9, and in molecular chain, the mol ratio of A segment and B segment is 9: 5.05; fusing point is 110 ℃; tensile strength is 46MPa, and elongation at break is 410%, and shock strength is 7KJ/m ².

Embodiment 11, prepare biodegradable polyester-polycarbonate segmented copolymer

Adopt and the identical reactant of embodiment 10 and preparation condition, only by HDI, change chainextender into hexaphenyl ring three silazane, chain extending reaction catalyzer changes dimethyl cetylamine into by stannous octoate, the consumption of this chain extending reaction catalyzer is 1g, after completion of the reaction, obtain Biodegradable polyester-polycarbonate block copolymer provided by the invention, its number-average molecular weight is 68, 500, molecular weight distribution is 3.9, in molecular chain, the mol ratio of A segment and B segment is 9.03: 5, fusing point is 105 ℃, tensile strength is 52MPa, elongation at break is 900%, sample punching constantly.

Embodiment 12, prepare biodegradable polyester-polycarbonate segmented copolymer

This embodiment adopts scorification to be prepared with twin screw extruder, and polyester prepolyer used is by the step 1 of embodiment 4) prepare, polycarbonate prepolymer used is prepared by embodiment 8.The parameter setting of this twin screw extruder is as follows:

Polyester prepolyer used, polycarbonate prepolymer, HDI, chain extending reaction catalyst of triethylamine are added to double-screw reactor by feeder and volume pump respectively, by regulating the frequency of feeder and volume pump, control material, the mol ratio of polyester prepolyer, polycarbonate prepolymer, HDI is 9: 1: 14, be total to 2000g, the consumption of chain extending reaction catalyzer is 5% of prepolymer total mass, twin-screw extrusion, cooling, pelletizing, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention.Its number-average molecular weight is 79,400, and molecular weight distribution is 1.9, and in molecular chain, the mol ratio of A segment and B segment is 9.08: 1, and fusing point is 113 ℃, and tensile strength is 45MPa, and elongation at break is 780%, and shock strength is 20kJ/m ².

Embodiment 13, prepare biodegradable polyester-polycarbonate segmented copolymer

In this embodiment, polyester prepolyer used is by the step 1 of embodiment 5) prepare, polycarbonate prepolymer used is prepared by embodiment 7.

Polyester prepolyer used, polycarbonate prepolymer, succinyl oxide, the sub-tin of chain extending reaction octoate catalyst are added to double-screw reactor by feeder and volume pump respectively, by regulating the frequency of feeder and volume pump, control material, the mol ratio of polyester prepolyer, polycarbonate prepolymer, succinyl oxide 3: 7: 13, be total to 2000g, the consumption of chain extending reaction catalyzer is 0.6% of prepolymer total mass.The parameter setting of twin screw extruder is as follows:

Twin-screw extrusion, cooling, pelletizing, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is 49,200, molecular weight distribution is 1.6, and in molecular chain, the mol ratio of A segment and B segment is 3: 7.08, fusing point is 96 ℃, tensile strength is 59MPa, and elongation at break is 610%, and shock strength is 18kJ/m ².

Embodiment 14, prepare biodegradable polyester-polycarbonate segmented copolymer

In this embodiment, the proportioning of each reactant is identical with embodiment 7, and the parameter setting of twin screw extruder used is as follows:

Twin-screw extrusion, cooling, pelletizing, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is 97,600, molecular weight distribution is 2.9, and in molecular chain, the mol ratio of A segment and B segment is 1: 5.09, and tensile strength is 47MPa, elongation at break is 770%, and shock strength is 22KJ/m ².

Embodiment 15, prepare biodegradable polyester-polycarbonate segmented copolymer

In this embodiment, the proportioning of each reactant is identical with embodiment 7, and the parameter setting of twin screw extruder used is as follows:

Twin-screw extrusion, cooling, pelletizing, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is 129,600, molecular weight distribution is 3.9, and in molecular chain, the mol ratio of A segment and B segment is 1: 5.06, and tensile strength is 37MPa, elongation at break is 570%, and shock strength is 32KJ/m ².

Embodiment 16, prepare biodegradable polyester-polycarbonate segmented copolymer

In this embodiment, the proportioning of each reactant is identical with embodiment 7, and the parameter setting of twin screw extruder used is as follows:

Twin-screw extrusion, cooling, pelletizing, obtain biodegradable polyester-polycarbonate segmented copolymer provided by the invention, its number-average molecular weight is 368,600, molecular weight distribution is 2.9, and in molecular chain, the mol ratio of A segment and B segment is 1: 5.03, and tensile strength is 57MPa, elongation at break is 870%, and shock strength is 32KJ/m ²; And the tensile strength of existing PBS homopolymer is only 32.7MPa, elongation at break is 190%, and shock strength is only 3.8KJ/m ², known polyester-polycarbonate segmented copolymer provided by the invention can significantly improve the erosion-resisting characteristics of PBS.

Claims (23)

1. the AB block copolymer being formed by A segment and B segment; Wherein, described A segment is hydroxy-end capped polyester prepolyer, and described B segment is hydroxy-end capped polycarbonate prepolymer; The number-average molecular weight of described A segment is 500-50,000;

The number-average molecular weight of described B segment is 500-50,000; The mol ratio of described A segment and B segment is 10:90-95:5;

The number-average molecular weight of described AB block copolymer is 5,000～500,000, and molecular weight distribution is 1-6;

Described AB block copolymer prepares according to the method comprising the steps:

1) aliphatic dibasic acid that is 2-12 by the total number of carbon atoms and the total number of carbon atoms are that the aliphatic dihydroxy alcohol of 2-12 carries out esterification, carry out after completion of the reaction polycondensation again, react the complete hydroxy-end capped polyester prepolyer that obtains;

2) aliphatic dihydroxy alcohol that is 2-12 by carbonic acid dibasic ester, described the total number of carbon atoms and catalyst for ester exchange reaction mix and carry out transesterification reaction, carry out after completion of the reaction polycondensation again, react the complete hydroxy-end capped polycarbonate prepolymer that obtains;

3) by hydroxy-end capped polyester prepolyer and the step 2 of step 1) gained) the hydroxy-end capped polycarbonate prepolymer of gained carries out chain extension copolyreaction under the effect of chainextender, reacts the complete described AB block copolymer that obtains.

2. segmented copolymer according to claim 1, is characterized in that: the number-average molecular weight of described A segment is 500-35 000;

The number-average molecular weight of described B segment is 1,000-35,000; The mol ratio of described A segment and B segment is 20:80-95:5;

The number-average molecular weight of described AB block copolymer is 10,000-40,000, and molecular weight distribution is 1.2-4.; Fusing point is 92-110 ℃, tensile strength 20-59MPa, and elongation at break is 102-980%, shock strength is 5.1-41KJ/m ².

3. segmented copolymer according to claim 2, is characterized in that: the number-average molecular weight of described A segment is 1,000-20 000;

The number-average molecular weight of described B segment is 2,000-30,000;

The number-average molecular weight of described AB block copolymer is 20,000-30,000, and molecular weight distribution is 1.5-4.

4. according to the segmented copolymer described in claim 1-3 any one, it is characterized in that: the aliphatic dibasic acid that described the total number of carbon atoms is 2-12 is selected from least one in oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, sebacic acid and dodecanedioic acid; Described the total number of carbon atoms is that the aliphatic dihydroxy alcohol of 2-12 is all selected from ethylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1, at least one in 6-hexylene glycol, decamethylene-glycol, 1,4 cyclohexane dimethanol, diethylene glycol and Triethylene glycol;

Described carbonic acid dibasic ester is selected from least one in methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and diphenyl carbonate;

Described catalyst for ester exchange reaction is selected from least one in the alkoxyl group germanium that the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, tin alkyl that the total number of carbon atoms is 4-40, alkoxyl group tin that the total number of carbon atoms is 4-40, alkyl germanium that the total number of carbon atoms is 4-40 and the total number of carbon atoms are 4-40;

Described chainextender is selected from least one in the two lactan of di-epoxy compounds, bisoxazoline, vulcabond, polycarbodiimide, two phthalic imidine, carboxylic acid anhydride, dicyclo imines ester, organosilazanes and diacyl.

5. segmented copolymer according to claim 4, is characterized in that: the aliphatic dibasic acid that described the total number of carbon atoms is 2-12 is selected from least one in oxalic acid, succsinic acid and hexanodioic acid; Described the total number of carbon atoms is that the aliphatic dihydroxy alcohol of 2-12 is all selected from ethylene glycol, BDO, 1, at least one in 6-hexylene glycol and 1,4 cyclohexane dimethanol;

Described carbonic acid dibasic ester is selected from least one in methylcarbonate, diethyl carbonate and diphenyl carbonate;

Described catalyst for ester exchange reaction is selected from least one in glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, manganese acetate and stannous octoate;

The described chainextender diacid two (3,4-epoxycyclohexyl methyl esters) of selecting oneself, N, N-diepoxy propyl benzamide, uracil, malonylurea, N-N-diepoxy propyl group imide, N-N-diepoxy propyl imidazole quinoline ketone, 2,2-two (2-bisoxazoline), tolylene diisocyanate, diphenylmethanediisocyanate, polymerization diphenylmethanediisocyanate, methylene-bis (4-cyclohexyl isocyanate), hexamethylene-diisocyanate, dicyclohexyl methyl hydride-4-4 '-vulcabond, 2,2,4-trimethyl cyclohexane vulcabond, two (phthalic imidines), 1,2,4,5-benzene tertacarbonic acid dianhydride, phthalic anhydride, succinyl oxide, Shuan bis-azolactone or bi-benzoxazine, octamethylcyclotetrasilazane, hexaphenyl three silazane, N, the two pyrrolidone of N '-phosphinylidyne, N, the two hexanolactams of N '-phosphinylidyne, N, the two laurolactams of N '-phosphinylidyne, N, the two pyrrolidone of N '-oxalyl, N, the two hexanolactams of N '-oxalyl, N, the two laurolactams of N '-oxalyl, N, the two pyrrolidone of N '-succinyl, N, the two pyrrolidone of N '-hexanedioyl, N, the two lactan of N '-hexanedioyl, N, the two pyrrolidone of N '-phthalyl, N, the two laurolactams of N '-phthalyl, N, the two tetramethyleneimine of N '-paraphenylene terephthalamide and N, at least one in the two laurolactams of N '-paraphenylene terephthalamide.

6. according to the segmented copolymer described in any one in claim 1-3, it is characterized in that: in described step 1), the molar ratio of the aliphatic dibasic acid that the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and the total number of carbon atoms are 2-12 is 3.0-1.0; In described step of esterification, temperature is 100-300 ℃, and the time is 2-20 hour; In described polycondensation steps, temperature is 150-300 ℃, and the time is 1-20 hour, and vacuum tightness is 1Pa～3 * 10 ⁴pa;

Described step 2), in, the molar ratio of the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and described carbonic acid dibasic ester is 3.0-1.0; The consumption of described catalyst for ester exchange reaction is the 0-2% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described catalyst for ester exchange reaction is not 0; In described transesterification steps, temperature is 70-300 ℃, and the time is 2-20 hour; In described polycondensation steps, temperature is 150-280 ℃, and the time is 1-20 hour, and vacuum tightness is 1Pa～3 * 10 ⁴pa;

In described step 3), the ratio of the mole dosage sum that feeds intake of described chainextender and described hydroxy-end capped polyester prepolyer and described polycarbonate prepolymer is 0.3～6.

7. segmented copolymer according to claim 6, is characterized in that: in described step 1), the molar ratio of the aliphatic dibasic acid that the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and the total number of carbon atoms are 2-12 is 2.0-1.0; In described step of esterification, temperature is 110-260 ℃, and the time is 3-15 hour; In described polycondensation steps, temperature is 150-280 ℃, and the time is 1-10 hour, and vacuum tightness is 1Pa～2 * 10 ⁴pa;

Described step 2), in, the molar ratio of the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and described carbonic acid dibasic ester is 2.0-1.0; The consumption of described catalyst for ester exchange reaction is the 0-0.6% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described catalyst for ester exchange reaction is not 0; In described transesterification steps, temperature is 80-230 ℃, and the time is 3-15 hour; In described polycondensation steps, temperature is 150-250 ℃, and the time is 1-10 hour, and vacuum tightness is 1Pa～2 * 10 ⁴pa;

In described step 3), the ratio of the mole dosage sum that feeds intake of described chainextender and described hydroxy-end capped polyester prepolyer and described polycarbonate prepolymer is 0.5～4.

8. according to the segmented copolymer described in any one in claim 1-3, it is characterized in that: described in described step 1), before step of esterification, also add catalyst for esterification reaction; Described catalyst for esterification reaction is selected from least one in the alkoxyl group germanium that the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, tin alkyl that the total number of carbon atoms is 4-40, alkoxyl group tin that the total number of carbon atoms is 4-40, alkyl germanium that the total number of carbon atoms is 4-40 and the total number of carbon atoms are 4-40; The consumption of described catalyst for esterification reaction is that described the total number of carbon atoms is the 0-2% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described catalyst for esterification reaction is not 0;

After described step 1) step of esterification before polycondensation steps, and described step 2) after transesterification steps before described polycondensation steps, all also can add polycondensation catalyst, described polycondensation catalyst is all selected from the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, the total number of carbon atoms is the tin alkyl of 4-40, the total number of carbon atoms is the alkoxyl group tin of 4-40, the total number of carbon atoms is the alkyl germanium of 4-40, the total number of carbon atoms is the alkoxyl group germanium of 4-40, the total number of carbon atoms is the zinc alkyl(s) of 4-40, the total number of carbon atoms is the alkoxyl group zinc of 4-40 and at least one in iron lactate, in described step 1), the consumption of polycondensation catalyst is that described the total number of carbon atoms is the 0-2% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described polycondensation catalyst is not 0, described step 2) in, the consumption of polycondensation catalyst is the 0-2% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described polycondensation catalyst is not 0,

Described step 2), afterwards before step 3) chain extension copolyreaction step, also can add chain extending reaction catalyzer; Described chain extending reaction catalyzer is selected from least one in tertiary amines chemicals, mineral acid, metal, metal oxide, metal chloride, metal acetate salt, organic titanic compound, organic germanium compounds, organo-tin compound, organo-aluminium compound and organoiron compound; The consumption of described chain extending reaction catalyzer is 0～5% of described hydroxy-end capped polyester prepolyer and described hydroxy-end capped polycarbonate prepolymer quality sum, and the consumption of described chain extending reaction catalyzer is not 0.

9. segmented copolymer according to claim 8, is characterized in that: described in described step 1), before step of esterification, also add catalyst for esterification reaction; Described catalyst for esterification reaction is selected from least one in glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, manganese acetate and stannous octoate; The consumption of described catalyst for esterification reaction is that described the total number of carbon atoms is the 0-0.6% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described catalyst for esterification reaction is not 0;

After described step 1) step of esterification before polycondensation steps, and described step 2) after transesterification steps before described polycondensation steps, all also can add polycondensation catalyst; Described polycondensation catalyst is all selected from least one in glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, manganese acetate and stannous octoate; In described step 1), the consumption of polycondensation catalyst is that described the total number of carbon atoms is the 0-0.6% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described polycondensation catalyst is not 0; Described step 2) in, the consumption of polycondensation catalyst is the 0-0.6% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described polycondensation catalyst is not 0;

Described step 2), afterwards before step 3) chain extension copolyreaction step, also can add chain extending reaction catalyzer; Described chain extending reaction catalyzer is selected from least one in triethylamine, dimethyl cetylamine, stannous octoate, tributyltin chloride, dibutyltin dilaurate, phosphonic acids calcium, lithium chloride, anhydrous zinc acetate, Zinc Undecylenate and zinc soap; The consumption of described chain extending reaction catalyzer is 0～4% of described hydroxy-end capped polyester prepolyer and described hydroxy-end capped polycarbonate prepolymer quality sum, and the consumption of described chain extending reaction catalyzer is not 0.

10. according to the segmented copolymer described in any one in claim 1-3, it is characterized in that: the reaction unit of described chain extension copolyreaction is reactor or twin screw extruder.

11. segmented copolymers according to claim 10, is characterized in that: in described reactor, carry out in described chain extending reaction step, temperature is 80-200 ℃, and the time is 0.5-6 hour;

In described twin screw extruder, carry out in described chain extension copolyreaction step, extruder temperature is 100-280 ℃, and screw speed is 5-500r/min, and the residence time is 0.5-30min; In described twin screw extruder, carry out in described chain extension copolyreaction step, the temperature of ZhiIV district, screw rod I district and head is followed successively by: 100-220 ℃, 100-280 ℃, 100-280 ℃, 100-280 ℃ and 100-220 ℃.

12. segmented copolymers according to claim 11, is characterized in that: in described reactor, carry out in described chain extending reaction step, temperature is 90～190 ℃, and the time is 0.5-5 hour;

In described twin screw extruder, carry out in described chain extension copolyreaction step, extruder temperature is 100-250 ℃, and screw speed is 30-300r/min, and the residence time is 2-15min; In described twin screw extruder, carry out in described chain extension copolyreaction step, the temperature of ZhiIV district, screw rod I district and head is followed successively by: 110-200 ℃, 120-200 ℃, 130-250 ℃, 130-200 ℃ and 100-200 ℃.

13. 1 kinds of methods of preparing the arbitrary described segmented copolymer of claim 1-3, comprise the steps:

1) aliphatic dibasic acid that is 2-12 by the total number of carbon atoms and the total number of carbon atoms are that the aliphatic dihydroxy alcohol of 2-12 carries out esterification, carry out after completion of the reaction polycondensation again, react the complete hydroxy-end capped polyester prepolyer that obtains;

2) aliphatic dihydroxy alcohol that is 2-12 by carbonic acid dibasic ester, described the total number of carbon atoms and catalyst for ester exchange reaction mix and carry out transesterification reaction, carry out after completion of the reaction polycondensation again, react the complete hydroxy-end capped polycarbonate prepolymer that obtains;

3) by hydroxy-end capped polyester prepolyer and the step 2 of step 1) gained) the hydroxy-end capped polycarbonate prepolymer of gained carries out chain extension copolyreaction under the effect of chainextender, reacts the complete described segmented copolymer that obtains.

14. methods according to claim 13, is characterized in that: the aliphatic dibasic acid that described the total number of carbon atoms is 2-12 is selected from least one in oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, sebacic acid and dodecanedioic acid; Described the total number of carbon atoms is that the aliphatic dihydroxy alcohol of 2-12 is all selected from ethylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1, at least one in 6-hexylene glycol, decamethylene-glycol, 1,4 cyclohexane dimethanol, diethylene glycol and Triethylene glycol;

Described carbonic acid dibasic ester is selected from least one in methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and diphenyl carbonate;

Described catalyst for ester exchange reaction is selected from least one in the alkoxyl group germanium that the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, tin alkyl that the total number of carbon atoms is 4-40, alkoxyl group tin that the total number of carbon atoms is 4-40, alkyl germanium that the total number of carbon atoms is 4-40 and the total number of carbon atoms are 4-40;

Described chainextender is selected from least one in the two lactan of di-epoxy compounds, bisoxazoline, vulcabond, polycarbodiimide, two phthalic imidine, carboxylic acid anhydride, dicyclo imines ester, organosilazanes and diacyl.

15. methods according to claim 14, is characterized in that: the aliphatic dibasic acid that described the total number of carbon atoms is 2-12 is selected from least one in oxalic acid, succsinic acid and hexanodioic acid; Described the total number of carbon atoms is that the aliphatic dihydroxy alcohol of 2-12 is all selected from ethylene glycol, BDO, 1, at least one in 6-hexylene glycol and 1,4 cyclohexane dimethanol;

Described carbonic acid dibasic ester is selected from least one in methylcarbonate, diethyl carbonate and diphenyl carbonate;

Described catalyst for ester exchange reaction is selected from least one in glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, manganese acetate and stannous octoate;

The described chainextender diacid two (3,4-epoxycyclohexyl methyl esters) of selecting oneself, N, N-diepoxy propyl benzamide, uracil, malonylurea, N-N-diepoxy propyl group imide, N-N-diepoxy propyl imidazole quinoline ketone, 2,2-two (2-bisoxazoline), tolylene diisocyanate, diphenylmethanediisocyanate, polymerization diphenylmethanediisocyanate, methylene-bis (4-cyclohexyl isocyanate), hexamethylene-diisocyanate, dicyclohexyl methyl hydride-4-4 '-vulcabond, 2,2,4-trimethyl cyclohexane vulcabond, two (phthalic imidines), 1,2,4,5-benzene tertacarbonic acid dianhydride, phthalic anhydride, succinyl oxide, Shuan bis-azolactone or bi-benzoxazine, octamethylcyclotetrasilazane, hexaphenyl three silazane, N, the two pyrrolidone of N '-phosphinylidyne, N, the two hexanolactams of N '-phosphinylidyne, N, the two laurolactams of N '-phosphinylidyne, N, the two pyrrolidone of N '-oxalyl, N, the two hexanolactams of N '-oxalyl, N, the two laurolactams of N '-oxalyl, N, the two pyrrolidone of N '-succinyl, N, the two pyrrolidone of N '-hexanedioyl, N, the two lactan of N '-hexanedioyl, N, the two pyrrolidone of N '-phthalyl, N, the two laurolactams of N '-phthalyl, N, the two tetramethyleneimine of N '-paraphenylene terephthalamide and N, at least one in the two laurolactams of N '-paraphenylene terephthalamide.

16. methods according to claim 13, is characterized in that: in described step 1), the molar ratio of the aliphatic dibasic acid that the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and the total number of carbon atoms are 2-12 is 3.0-1.0; In described step of esterification, temperature is 100-300 ℃, and the time is 2-20 hour; In described polycondensation steps, temperature is 150-300 ℃, and the time is 1-20 hour, and vacuum tightness is 1Pa～3 * 10 ⁴pa;

Described step 2), in, the molar ratio of the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and described carbonic acid dibasic ester is 3.0-1.0; The consumption of described catalyst for ester exchange reaction is the 0-2% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described catalyst for ester exchange reaction is not 0; In described transesterification steps, temperature is 70-300 ℃, and the time is 2-20 hour; In described polycondensation steps, temperature is 150-280 ℃, and the time is 1-20 hour, and vacuum tightness is 1Pa～3 * 10 ⁴pa;

In described step 3), the ratio of the mole dosage sum that feeds intake of described chainextender and described hydroxy-end capped polyester prepolyer and described polycarbonate prepolymer is 0.3～6.

17. methods according to claim 16, is characterized in that: in described step 1), the molar ratio of the aliphatic dibasic acid that the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and the total number of carbon atoms are 2-12 is 2.0-1.0; In described step of esterification, temperature is 110-260 ℃, and the time is 3-15 hour; In described polycondensation steps, temperature is 150-280 ℃, and the time is 1-10 hour, and vacuum tightness is 1Pa～2 * 10 ⁴pa;

Described step 2), in, the molar ratio of the aliphatic dihydroxy alcohol that described the total number of carbon atoms is 2-12 and described carbonic acid dibasic ester is 2.0-1.0; The consumption of described catalyst for ester exchange reaction is the 0-0.6% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described catalyst for ester exchange reaction is not 0; In described transesterification steps, temperature is 80-230 ℃, and the time is 3-15 hour; In described polycondensation steps, temperature is 150-250 ℃, and the time is 1-10 hour, and vacuum tightness is 1Pa～2 * 10 ⁴pa;

In described step 3), the ratio of the mole dosage sum that feeds intake of described chainextender and described hydroxy-end capped polyester prepolyer and described polycarbonate prepolymer is 0.5～4.

18. methods according to claim 13, is characterized in that: described in described step 1), before step of esterification, also add catalyst for esterification reaction; Described catalyst for esterification reaction is selected from least one in the alkoxyl group germanium that the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, tin alkyl that the total number of carbon atoms is 4-40, alkoxyl group tin that the total number of carbon atoms is 4-40, alkyl germanium that the total number of carbon atoms is 4-40 and the total number of carbon atoms are 4-40; The consumption of described catalyst for esterification reaction is that described the total number of carbon atoms is the 0-2% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described catalyst for esterification reaction is not 0;

After described step 1) step of esterification before polycondensation steps, and described step 2) after transesterification steps before described polycondensation steps, all also can add polycondensation catalyst, described polycondensation catalyst is all selected from the vitriol oil, tosic acid, glass putty, antimonous oxide, antimony glycol, antimony acetate, germanium dioxide, germanium chloride, tin tetrachloride, magnesium acetate, zinc acetate, manganese acetate, salt of wormwood, sodium carbonate, calcium carbonate, sodium bicarbonate, saleratus, the total number of carbon atoms is the tin alkyl of 4-40, the total number of carbon atoms is the alkoxyl group tin of 4-40, the total number of carbon atoms is the alkyl germanium of 4-40, the total number of carbon atoms is the alkoxyl group germanium of 4-40, the total number of carbon atoms is the zinc alkyl(s) of 4-40, the total number of carbon atoms is the alkoxyl group zinc of 4-40 and at least one in iron lactate, in described step 1), the consumption of polycondensation catalyst is that described the total number of carbon atoms is the 0-2% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described polycondensation catalyst is not 0, described step 2) in, the consumption of polycondensation catalyst is the 0-2% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described polycondensation catalyst is not 0,

Described step 2), afterwards before step 3) chain extension copolyreaction step, also can add chain extending reaction catalyzer; Described chain extending reaction catalyzer is selected from least one in tertiary amines chemicals, mineral acid, metal, metal oxide, metal chloride, metal acetate salt, organic titanic compound, organic germanium compounds, organo-tin compound, organo-aluminium compound and organoiron compound; The consumption of described chain extending reaction catalyzer is 0～5% of described hydroxy-end capped polyester prepolyer and described hydroxy-end capped polycarbonate prepolymer quality sum, and the consumption of described chain extending reaction catalyzer is not 0.

19. methods according to claim 18, is characterized in that: described in described step 1), before step of esterification, also add catalyst for esterification reaction; Described catalyst for esterification reaction is selected from least one in glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, manganese acetate and stannous octoate; The consumption of described catalyst for esterification reaction is that described the total number of carbon atoms is the 0-0.6% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described catalyst for esterification reaction is not 0;

After described step 1) step of esterification before polycondensation steps, and described step 2) after transesterification steps before described polycondensation steps, all also can add polycondensation catalyst; Described polycondensation catalyst is all selected from least one in glass putty, antimonous oxide, butyl (tetra) titanate, salt of wormwood, sodium bicarbonate, saleratus, germanium dioxide, zinc acetate, manganese acetate and stannous octoate; In described step 1), the consumption of polycondensation catalyst is that described the total number of carbon atoms is the 0-0.6% of the aliphatic dibasic acid of 2-12 and the aliphatic dihydroxy alcohol quality sum that the total number of carbon atoms is 2-12, and the consumption of described polycondensation catalyst is not 0; Described step 2) in, the consumption of polycondensation catalyst is the 0-0.6% of described carbonic acid dibasic ester and the total number of carbon atoms aliphatic dihydroxy alcohol quality sum that is 2-12, and the consumption of described polycondensation catalyst is not 0;

Described step 2), afterwards before step 3) chain extension copolyreaction step, also can add chain extending reaction catalyzer; Described chain extending reaction catalyzer is selected from least one in triethylamine, dimethyl cetylamine, stannous octoate, tributyltin chloride, dibutyltin dilaurate, phosphonic acids calcium, lithium chloride, anhydrous zinc acetate, Zinc Undecylenate and zinc soap; The consumption of described chain extending reaction catalyzer is 0～4% of described hydroxy-end capped polyester prepolyer and described hydroxy-end capped polycarbonate prepolymer quality sum, and the consumption of described chain extending reaction catalyzer is not 0.

20. methods according to claim 13, is characterized in that: the reaction unit of described chain extension copolyreaction is reactor or twin screw extruder.

21. methods according to claim 20, is characterized in that: in described reactor, carry out in described chain extending reaction step, temperature is 80-200 ℃, and the time is 0.5-6 hour;

In described twin screw extruder, carry out in described chain extension copolyreaction step, extruder temperature is 100-280 ℃, and screw speed is 5-500r/min, and the residence time is 0.5-30min; In described twin screw extruder, carry out in described chain extension copolyreaction step, the temperature of ZhiIV district, screw rod I district and head is followed successively by: 100-220 ℃, 100-280 ℃, 100-280 ℃, 100-280 ℃ and 100-220 ℃.

22. methods according to claim 21, is characterized in that: in described reactor, carry out in described chain extending reaction step, temperature is 90～190 ℃, and the time is 0.5-5 hour;

In described twin screw extruder, carry out in described chain extension copolyreaction step, extruder temperature is 100-250 ℃, and screw speed is 30-300r/min, and the residence time is 2-15min; In described twin screw extruder, carry out in described chain extension copolyreaction step, the temperature of ZhiIV district, screw rod I district and head is followed successively by: 110-200 ℃, 120-200 ℃, 130-250 ℃, 130-200 ℃ and 100-200 ℃.

The application of the arbitrary described segmented copolymer of 23. claim 1-12 in preparing the impact modifier of biodegradated polymer materal.