CN103467713A

CN103467713A - Low-carboxylated biodegradable polyester and production method thereof

Info

Publication number: CN103467713A
Application number: CN2013103969525A
Authority: CN
Inventors: 丁建萍; 潘哆吉; 陈文生; 孙建新; 任英杰; 李旭娟; 姜天伟
Original assignee: XINJIANG GENERAL PLASTICS HIGH PERFORMANCE ENGINEERING TECHNOLOGY RESEARCH CENTER (CO LTD); XINJIANG BLUE RIDGE TUNHE CHEMICAL INDUSTRY Co Ltd
Current assignee: Xinjiang weigerui Biotechnology Co.,Ltd.
Priority date: 2013-09-04
Filing date: 2013-09-04
Publication date: 2013-12-25
Anticipated expiration: 2033-09-04
Also published as: CN103467713B

Abstract

The invention relates to the technical field of polyester high-molecular materials, and particularly relates to a low-carboxylated biodegradable polyester and a production method thereof. The low-carboxylated biodegradable polyester comprises1,6-adipic acid or/and terephthalic acid and 1,4-butanediol. According to the preparation method of the low-carboxylated biodegradable polyester, the content of carboxyl end groups in the polyester can be furthest reduced by adopting a compound titanium catalyst and a carboxyl scavenger to produce condensation polymerization in the later period of esterification; the catalytic activity of titanium catalyst can be controlled by adding chelate with stabilizing effect, so as to avoid the side degradation reaction caused by the high activity of the catalyst in the later period of condensation reaction and furthest reduce the side reaction in the later period of the condensation reaction, so that the low-carboxylated level of the finished polyester product can be guaranteed, other additives are not additionally needed for modifying the product, the content of carboxyl end groups in the product can be reduced, and the high production cost of the product can be avoided.

Description

Carboxy lower Biodegradable polyester and production method thereof

Technical field

the present invention relates to the polyester technical field of polymer materials, is a kind of carboxy lower Biodegradable polyester and production method thereof.

Background technology

nowadays, plastics are to form a class material of important complementation with materials such as timber, iron and steel, pottery, cement, have obtained application very widely, are greatly changing our life.But the use of conventional plastic has caused serious " white pollution ", this comes from people when focusing on the performance of conventional plastic goods, has ignored its environment property received.Conventional plastic can be detained decades in environment, even go up a century also is difficult to thorough degraded.Increasingly serious " white ecological pollution " problem has made the friendly plastic product of development environment become the common recognition of countries in the world.Under the support of various incentive policies, main Polymer production enterprise has in the world developed multiple degradative plastics product.Commodity " Ecoflex " resin by name of Germany's BASF exploitation is exactly Typical Representative wherein, its chemistry " polybutylene terephthalate-altogether-poly adipate succinic acid ester (PBAT) " by name, be the random copolymers obtained through high-temperature polycondensation by terephthalic acid, hexanodioic acid and butyleneglycol, belong to the biodegradable plastic of mechanical property and degradation property excellence.This resinoid, under certain wet heat condition, can slowly be degraded, and first generates the polymer segments that end group is carboxyl and hydroxyl.Afterwards, particularly hold the existence of carboxyl and can accelerate widely the degradation rate of polyester due to more end group.Final process microbial process becomes carbonic acid gas and water.If under composting conditions, the degradation rate of this polymkeric substance is faster.So PBAT is the friendly macromolecular material that a class environment can receive.But this degradation characteristic also causes its use under some hygrothermal environments to be subject to great restriction, as agricultural mulching.For this reason, just must try every possible means to reduce the end group in this resinoid product, particularly hold the content of carboxyl, to improve this resinoid anti-hydrolytic performance, thereby delay degradation rate, to guarantee material mechanical performance and the duration of service under certain working conditions.In the Chinese patent literature that publication number is 102165012, announced a kind of by vinylbenzene, acrylate and/or methacrylic ester containing epoxy group(ing) multipolymer and acidic substance scavenging agent under certain condition with the Biodegradable polyester blend, to improve the method for Biodegradable polyester hydrolytic resistance and melt viscosity.But, the mode of this blend has increased the cost of product on the one hand, easily causes in the course of processing that on the other hand the product look becomes and Partial digestion, in addition, the acid cleaner used overflows as carbodiimide compound has irritant gas in the process of high temperature process and use, affects environment.Announced a kind of method that solves the aliphatic-aromatic copolyester hydrolytic resistance in polymerization process in the Chinese patent literature that publication number is 102131868, specific practice is first to prepare respectively aliphatics and aromatic ester compound, then two kinds of carboxylates are mixed, then add phosphorous ground oxidation inhibitor and carbonate or carbonates material to reach the hydrophobic purpose of final polyester product.Although this method has been avoided the product cost problem increased because of blending and modifying,, two step esterification process have also increased the cost of product, simultaneously, improper if the polymerization degree is controlled, just can exert an influence to the biodegradability of the finished product.

Summary of the invention

the invention provides a kind of carboxy lower Biodegradable polyester and production method thereof, overcome the deficiency of above-mentioned prior art, it can effectively solve existing technology production cost height and the unsettled problem of product performance when reducing the Biodegradable polyester degradation rate.

one of technical scheme of the present invention realizes by following measures: a kind of carboxy lower Biodegradable polyester, comprise that raw materials by weight portion consists of 40 parts to 100 part 1, the 6-hexanodioic acid is or/and 1 part to 60 parts terephthalic acid and 80 parts to 100 part 1, the 4-butyleneglycol, wherein, this carboxy lower Biodegradable polyester obtains as follows: the first step, desired raw material is placed in to reactor, and the temperature of material in reactor is raised to 80 ℃ to 100 ℃, then mixing of materials is added to metatitanic acid four butyl alcohol esters of raw material weight 50ppm to 250ppm after evenly, at pressure, be then-40KPa is to-80KPa, temperature is 225 ℃ to 230 ℃, carry out esterification under the condition that stir speed (S.S.) is 50r/min to 100r/min, when the esterification water parts by weight of collecting reach 15 parts to 55 parts, stop esterification, second step, after esterification finishes, pressure in reactor is adjusted to normal pressure, then to the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, add the carboxyl remover of raw material weight 30ppm to 1000ppm and the sequestrant of raw material weight 10ppm to 300ppm after mixing, at pressure, be then that 0.5 KPa to 2KPa, temperature are to carry out prepolymerization reaction under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 10NM to 100NM, prepolymerization reaction completes, the 3rd step, after prepolymerization reaction completes, at pressure, be that 0Pa to 100Pa, temperature are to carry out polycondensation under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 20NM to 80NM, stop polycondensation, after polycondensation finishes, use the nitrogen pressurization to get rid of the melt in reactor, with the cooling carboxy lower Biodegradable polyester that obtains of water-bath.

two of technical scheme of the present invention realizes by following measures: a kind of production method of carboxy lower Biodegradable polyester, raw materials by weight portion consists of 40 parts to 100 part 1, the 6-hexanodioic acid is or/and 1 part to 60 parts terephthalic acid and 80 parts to 100 part 1, the 4-butyleneglycol, wherein, the production method of this carboxy lower Biodegradable polyester obtains in the steps below: the first step, desired raw material is placed in to reactor, and the temperature of material in reactor is raised to 80 ℃ to 100 ℃, then mixing of materials is added to metatitanic acid four butyl alcohol esters of raw material weight 50ppm to 250ppm after evenly, at pressure, be then-40KPa is to-80KPa, temperature is 225 ℃ to 230 ℃, carry out esterification under the condition that stir speed (S.S.) is 50r/min to 100r/min, when the esterification water parts by weight of collecting reach 15 parts to 55 parts, stop esterification, second step, after esterification finishes, pressure in reactor is adjusted to normal pressure, then to the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, add the carboxyl remover of raw material weight 30ppm to 1000ppm and the sequestrant of raw material weight 10ppm to 300ppm after mixing, at pressure, be then that 0.5 KPa to 2KPa, temperature are to carry out prepolymerization reaction under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 10NM to 100NM, prepolymerization reaction completes, the 3rd step, after prepolymerization reaction completes, at pressure, be that 0Pa to 100Pa, temperature are to carry out polycondensation under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 20NM to 80NM, stop polycondensation, after polycondensation finishes, use the nitrogen pressurization to get rid of the melt in reactor, with the cooling carboxy lower Biodegradable polyester that obtains of water-bath.

below the further optimization and/or improvements to the foregoing invention technical scheme:

above-mentioned composite titanium series catalysts is counted the organic titanic compound that comprises 50 parts to 98 parts, the silicoorganic compound of 1 part to 50 parts and the metal salt compound of 1 part to 10 parts by weight, wherein, organic titanic compound is more than one in metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, metatitanic acid four propyl alcohol esters, metatitanic acid four butyl alcohol esters, titanium isopropylate, metatitanic acid four isobutyl alcohol esters, metatitanic acid four trimethyl carbinol esters, metatitanic acid four isooctyl alcohol esters, metatitanic acid Fourth Ring hexanol ester, metatitanic acid four benzylalcohol esters, cresols titanium, methyl ethyl diketone oxygen titanium, titanium ethylene glycolate, poly-metatitanic acid butyl alcohol ester etc., silicoorganic compound are trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, γ-aminopropyl methyldiethoxysilane, hexadecyl Trimethoxy silane, 3-aminopropyl triethoxysilane, vinyltriethoxysilane, methyl silicate, tetraethyl silicate, silicic acid propyl ester, butyl silicate, 1, more than one in two (trimethylsiloxy group) ethane of 2-, metal salt compound is more than one in lithium acetate, sodium acetate, lime acetate, cobaltous acetate, zinc acetate, manganous acetate, venus crystals, nickelous acetate, antimony acetate, acid chloride, lanthanum acetate, rubidium acetate, magnesium acetate, Magnesium Trisilicate, aluminum acetate, pure aluminium silicate, aluminium acetylacetonate, or/and, the carboxyl remover is Racemic glycidol, isopropyl glycidyl ether, n-butyl glycidyl ether, the n-octyl glycidyl ether, the dodecyl glycidyl ether, epoxy soybean oil, the cyclohexyl glycidyl ether, the benzyl glycidyl ether, furfuryl glycidyl ether, glycidyl allyl ether, glycidyl methacrylate, ethylene glycol diglycidylether, 1, the 4-butanediol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 2-cylohexanediol diglycidyl ether, 1, the 4-cylohexanediol diglycidyl ether, isocyanuric acid three-glycidyl ester, more than one in γ-glycidyl ether oxygen propyl trimethoxy silicane, or/and, inner complex is ethylene glycol, quadrol, butyleneglycol, 1, the 4-butanediamine, 2, the 2-dipyridyl, 2, 6-dicarboxyl pyridine, Dopamine HCL, α-amino isopropyl alcohol, diisopropanolamine (DIPA), tri-isopropanolamine, Diethylenetriaminee (DETA), triethylenetetramine, N, two (3-aminopropyl) quadrols of N'-, N-(2-hydroxyethyl) quadrol, N-acetyl quadrol, tetraacetyl ethylene diamine, N, the N-dimethyl-ethylenediamine, N, the N'-dimethyl-ethylenediamine, Tetramethyl Ethylene Diamine, N, the N'-diphenyl ethylene diamine, ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl-ethylenediamine-N, N', the N'-nitrilotriacetic, ethylene diamine tetra methylene phosphonic acid, polyvinyl alcohol, more than one in kollidon.

in the above-mentioned the first step, after first reactor being replaced with nitrogen, then raw material is placed in to reactor; Or/and, in the first step, after adding metatitanic acid four butyl alcohol esters, with nitrogen by be adjusted to-40KPa of the pressure in reactor to-80KPa; Or/and, in second step, esterification is adjusted to normal pressure with nitrogen by the pressure in reactor after finishing; Or/and, in second step, after adding the composite titanium series catalysts in reactor, with nitrogen, the pressure in reactor is adjusted to normal pressure to-80KPa; Or/and, in second step, after adding carboxyl remover and sequestrant in reactor, with nitrogen, the pressure of the prepolymerization reaction in reactor is adjusted to 0.5 KPa to 2KPa; Or/and, in the 3rd step, after prepolymerization reaction completes, with nitrogen, the pressure of polycondensation in reactor is adjusted to 0Pa to 100Pa.

in the above-mentioned the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of material in reactor is raised to 80 to 100 ℃; Or/and, in the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of charge in reactor is raised to 225 ℃ to 230 ℃ and carries out esterification.

in the above-mentioned the first step, in stir speed (S.S.), be that under 30r/min to 100r/min condition, stirring 30min is even by mixing of materials; Or/and, in second step, after the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, in stir speed (S.S.), be under 30r/min to 100r/min condition, to stir after 15min mixes to add carboxyl remover and sequestrant.

the present invention is by adopting composite titanium series catalysts and carboxyl scavenging agent to carry out polycondensation in the esterification later stage, can farthest reduce the content of carboxyl end group of carboxylate, add the inner complex with stabilization to control the catalytic activity of Titanium series catalyst simultaneously, the product degraded side reaction that the high reactivity of having avoided catalyzer caused in the polycondensation later stage, to reduce to greatest extent the side reaction in polycondensation later stage, thereby guarantee the carboxy lower level of final polyester product, thereby need not additionally add again other additives to carry out to product the content of carboxyl end group that modification reduces product, avoid causing the products production cost high.

Embodiment

the present invention is not subject to the restriction of following embodiment, can determine concrete embodiment according to technical scheme of the present invention and practical situation.Ppm in the present invention is 1,000,000/.

embodiment 1, this carboxy lower Biodegradable polyester, comprise that raw materials by weight portion consists of 40 parts to 100 part 1, the 6-hexanodioic acid is or/and 1 part to 60 parts terephthalic acid and 80 parts to 100 part 1, the 4-butyleneglycol, wherein, this carboxy lower Biodegradable polyester obtains by following production method: the first step, desired raw material is placed in to reactor, and the temperature of material in reactor is raised to 80 ℃ to 100 ℃, then mixing of materials is added to metatitanic acid four butyl alcohol esters of raw material weight 50ppm to 250ppm after evenly, at pressure, be then-40KPa is to-80KPa, temperature is 225 ℃ to 230 ℃, carry out esterification under the condition that stir speed (S.S.) is 50r/min to 100r/min, when the esterification water parts by weight of collecting reach 15 parts to 55 parts, stop esterification, second step, after esterification finishes, pressure in reactor is adjusted to normal pressure, then to the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, add the carboxyl remover of raw material weight 30ppm to 1000ppm and the sequestrant of raw material weight 10ppm to 300ppm after mixing, at pressure, be then that 0.5 KPa to 2KPa, temperature are to carry out prepolymerization reaction under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 10NM to 100NM, prepolymerization reaction completes, the 3rd step, after prepolymerization reaction completes, at pressure, be that 0Pa to 100Pa, temperature are to carry out polycondensation under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 20NM to 80NM, stop polycondensation, after polycondensation finishes, use the nitrogen pressurization to get rid of the melt in reactor, with the cooling carboxy lower Biodegradable polyester that obtains of water-bath.

embodiment 2, this carboxy lower Biodegradable polyester, comprise that raw materials by weight portion consists of 40 parts or 100 part 1, the 6-hexanodioic acid is or/and 1 part or 60 parts of terephthalic acids and 80 parts or 100 part 1, the 4-butyleneglycol, wherein, this carboxy lower Biodegradable polyester obtains by following production method: the first step, desired raw material is placed in to reactor, and the temperature of material in reactor is raised to 80 ℃ or 100 ℃, then mixing of materials is added to metatitanic acid four butyl alcohol esters of raw material weight 50ppm or 250ppm after evenly, at pressure, be then-40KPa or-80KPa, temperature is 225 ℃ or 230 ℃, carry out esterification under the condition that stir speed (S.S.) is 50r/min or 100r/min, when the esterification water parts by weight of collecting reach 15 parts or 55 parts, stop esterification, second step, after esterification finishes, pressure in reactor is adjusted to normal pressure, then to the composite titanium series catalysts that adds raw material weight 50ppm or 1000ppm in reactor, add the carboxyl remover of raw material weight 30ppm or 1000ppm and the sequestrant of raw material weight 10ppm or 300ppm after mixing, at pressure, be then that 0.5 KPa to 2KPa, temperature are to carry out prepolymerization reaction under 230 ℃ or 235 ℃, the stir speed (S.S.) condition that is 30r/min or 80r/min, when the stirring moment of torsion reaches 10NM or 100NM, prepolymerization reaction completes, the 3rd step, after prepolymerization reaction completes, at pressure, be that 0Pa or 100Pa, temperature are to carry out polycondensation under 230 ℃ or 235 ℃, the stir speed (S.S.) condition that is 30r/min or 80r/min, when the stirring moment of torsion reaches 20NM or 80NM, stop polycondensation, after polycondensation finishes, use the nitrogen pressurization to get rid of the melt in reactor, with the cooling carboxy lower Biodegradable polyester that obtains of water-bath.

embodiment 3, as above-described embodiment preferably, the composite titanium series catalysts is counted the organic titanic compound that comprises 50 parts to 98 parts by weight, the metal salt compound of the silicoorganic compound of 1 part to 50 parts and 1 part to 10 parts, wherein, organic titanic compound is metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, metatitanic acid four propyl alcohol esters, metatitanic acid four butyl alcohol esters, titanium isopropylate, metatitanic acid four isobutyl alcohol esters, metatitanic acid four trimethyl carbinol esters, metatitanic acid four isooctyl alcohol esters, metatitanic acid Fourth Ring hexanol ester, metatitanic acid four benzylalcohol esters, the cresols titanium, methyl ethyl diketone oxygen titanium, titanium ethylene glycolate, more than one in poly-metatitanic acid butyl alcohol ester etc., silicoorganic compound are trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, γ-aminopropyl methyldiethoxysilane, hexadecyl Trimethoxy silane, 3-aminopropyl triethoxysilane, vinyltriethoxysilane, methyl silicate, tetraethyl silicate, silicic acid propyl ester, butyl silicate, 1, more than one in two (trimethylsiloxy group) ethane of 2-, metal salt compound is more than one in lithium acetate, sodium acetate, lime acetate, cobaltous acetate, zinc acetate, manganous acetate, venus crystals, nickelous acetate, antimony acetate, acid chloride, lanthanum acetate, rubidium acetate, magnesium acetate, Magnesium Trisilicate, aluminum acetate, pure aluminium silicate, aluminium acetylacetonate, or/and, the carboxyl remover is Racemic glycidol, isopropyl glycidyl ether, n-butyl glycidyl ether, the n-octyl glycidyl ether, the dodecyl glycidyl ether, epoxy soybean oil, the cyclohexyl glycidyl ether, the benzyl glycidyl ether, furfuryl glycidyl ether, glycidyl allyl ether, glycidyl methacrylate, ethylene glycol diglycidylether, 1, the 4-butanediol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 2-cylohexanediol diglycidyl ether, 1, the 4-cylohexanediol diglycidyl ether, isocyanuric acid three-glycidyl ester, more than one in γ-glycidyl ether oxygen propyl trimethoxy silicane, or/and, inner complex is ethylene glycol, quadrol, butyleneglycol, 1, the 4-butanediamine, 2, the 2-dipyridyl, 2, 6-dicarboxyl pyridine, Dopamine HCL, α-amino isopropyl alcohol, diisopropanolamine (DIPA), tri-isopropanolamine, Diethylenetriaminee (DETA), triethylenetetramine, N, two (3-aminopropyl) quadrols of N'-, N-(2-hydroxyethyl) quadrol, N-acetyl quadrol, tetraacetyl ethylene diamine, N, the N-dimethyl-ethylenediamine, N, the N'-dimethyl-ethylenediamine, Tetramethyl Ethylene Diamine, N, the N'-diphenyl ethylene diamine, ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl-ethylenediamine-N, N', the N'-nitrilotriacetic, ethylene diamine tetra methylene phosphonic acid, polyvinyl alcohol, more than one in kollidon.

embodiment 4, as above-described embodiment preferably, in the first step, after first reactor being replaced with nitrogen, then raw material is placed in to reactor; Or/and, in the first step, after adding metatitanic acid four butyl alcohol esters, with nitrogen by be adjusted to-40KPa of the pressure in reactor to-80KPa; Or/and, in second step, esterification is adjusted to normal pressure with nitrogen by the pressure in reactor after finishing; Or/and, in second step, after adding the composite titanium series catalysts in reactor, with nitrogen, the pressure in reactor is adjusted to normal pressure to-80KPa; Or/and, in second step, after adding carboxyl remover and sequestrant in reactor, with nitrogen, the pressure of the prepolymerization reaction in reactor is adjusted to 0.5 KPa to 2KPa; Or/and, in the 3rd step, after prepolymerization reaction completes, with nitrogen, the pressure of polycondensation in reactor is adjusted to 0Pa to 100Pa.

embodiment 5, as above-described embodiment preferably, in the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of material in reactor is raised to 80 to 100 ℃; Or/and, in the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of charge in reactor is raised to 225 ℃ to 230 ℃ and carries out esterification.

embodiment 6, as above-described embodiment preferably, in the first step, in stir speed (S.S.), be that to stir 30min under 30r/min to 100r/min condition even by mixing of materials; Or/and, in second step, after the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, in stir speed (S.S.), be under 30r/min to 100r/min condition, to stir after 15min mixes to add carboxyl remover and sequestrant.

the content of carboxyl end group average value ranges of the carboxy lower Biodegradable polyester obtained according to the above embodiment of the present invention is 10.2 mol/t to 28mol/t, and the content of carboxyl end group average value ranges of the degraded polyester product obtained according to prior art is 28.5 mol/t to 57.6mol/t, this shows, the present invention is by adopting composite titanium series catalysts and carboxyl scavenging agent to carry out polycondensation in the esterification later stage, can farthest reduce the content of carboxyl end group of carboxylate, add the inner complex with stabilization to control the catalytic activity of Titanium series catalyst simultaneously, the product degraded side reaction that the high reactivity of having avoided catalyzer caused in the polycondensation later stage, to reduce to greatest extent the side reaction in polycondensation later stage, thereby guarantee the carboxy lower level of final polyester product, thereby need not additionally add again other additives to carry out to product the content of carboxyl end group that modification reduces product, avoid the problem that causes the products production cost high.

Claims

1. a carboxy lower Biodegradable polyester, it is characterized in that raw materials by weight portion consists of 40 parts to 100 part 1, the 6-hexanodioic acid is or/and 1 part to 60 parts terephthalic acid and 80 parts to 100 part 1, the 4-butyleneglycol, wherein, this carboxy lower Biodegradable polyester obtains as follows: the first step, desired raw material is placed in to reactor, and the temperature of material in reactor is raised to 80 ℃ to 100 ℃, then mixing of materials is added to metatitanic acid four butyl alcohol esters of raw material weight 50ppm to 250ppm after evenly, at pressure, be then-40KPa is to-80KPa, temperature is 225 ℃ to 230 ℃, carry out esterification under the condition that stir speed (S.S.) is 50r/min to 100r/min, when the esterification water parts by weight of collecting reach 15 parts to 55 parts, stop esterification, second step, after esterification finishes, pressure in reactor is adjusted to normal pressure, then to the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, add the carboxyl remover of raw material weight 30ppm to 1000ppm and the sequestrant of raw material weight 10ppm to 300ppm after mixing, at pressure, be then that 0.5 KPa to 2KPa, temperature are to carry out prepolymerization reaction under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 10NM to 100NM, prepolymerization reaction completes, the 3rd step, after prepolymerization reaction completes, at pressure, be that 0Pa to 100Pa, temperature are to carry out polycondensation under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 20NM to 80NM, stop polycondensation, after polycondensation finishes, use the nitrogen pressurization to get rid of the melt in reactor, with the cooling carboxy lower Biodegradable polyester that obtains of water-bath.

2. carboxy lower Biodegradable polyester according to claim 1, it is characterized in that the composite titanium series catalysts counts the organic titanic compound that comprises 50 parts to 98 parts by weight, the metal salt compound of the silicoorganic compound of 1 part to 50 parts and 1 part to 10 parts, wherein, organic titanic compound is metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, metatitanic acid four propyl alcohol esters, metatitanic acid four butyl alcohol esters, titanium isopropylate, metatitanic acid four isobutyl alcohol esters, metatitanic acid four trimethyl carbinol esters, metatitanic acid four isooctyl alcohol esters, metatitanic acid Fourth Ring hexanol ester, metatitanic acid four benzylalcohol esters, the cresols titanium, methyl ethyl diketone oxygen titanium, titanium ethylene glycolate, more than one in poly-metatitanic acid butyl alcohol ester etc., silicoorganic compound are trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, γ-aminopropyl methyldiethoxysilane, hexadecyl Trimethoxy silane, 3-aminopropyl triethoxysilane, vinyltriethoxysilane, methyl silicate, tetraethyl silicate, silicic acid propyl ester, butyl silicate, 1, more than one in two (trimethylsiloxy group) ethane of 2-, metal salt compound is more than one in lithium acetate, sodium acetate, lime acetate, cobaltous acetate, zinc acetate, manganous acetate, venus crystals, nickelous acetate, antimony acetate, acid chloride, lanthanum acetate, rubidium acetate, magnesium acetate, Magnesium Trisilicate, aluminum acetate, pure aluminium silicate, aluminium acetylacetonate, or/and, the carboxyl remover is Racemic glycidol, isopropyl glycidyl ether, n-butyl glycidyl ether, the n-octyl glycidyl ether, the dodecyl glycidyl ether, epoxy soybean oil, the cyclohexyl glycidyl ether, the benzyl glycidyl ether, furfuryl glycidyl ether, glycidyl allyl ether, glycidyl methacrylate, ethylene glycol diglycidylether, 1, the 4-butanediol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 2-cylohexanediol diglycidyl ether, 1, the 4-cylohexanediol diglycidyl ether, isocyanuric acid three-glycidyl ester, more than one in γ-glycidyl ether oxygen propyl trimethoxy silicane, or/and, inner complex is ethylene glycol, quadrol, butyleneglycol, 1, the 4-butanediamine, 2, the 2-dipyridyl, 2, 6-dicarboxyl pyridine, Dopamine HCL, α-amino isopropyl alcohol, diisopropanolamine (DIPA), tri-isopropanolamine, Diethylenetriaminee (DETA), triethylenetetramine, N, two (3-aminopropyl) quadrols of N'-, N-(2-hydroxyethyl) quadrol, N-acetyl quadrol, tetraacetyl ethylene diamine, N, the N-dimethyl-ethylenediamine, N, the N'-dimethyl-ethylenediamine, Tetramethyl Ethylene Diamine, N, the N'-diphenyl ethylene diamine, ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl-ethylenediamine-N, N', the N'-nitrilotriacetic, ethylene diamine tetra methylene phosphonic acid, polyvinyl alcohol, more than one in kollidon.

3. carboxy lower Biodegradable polyester according to claim 1 and 2, is characterized in that in the first step, after first reactor being replaced with nitrogen, then raw material is placed in to reactor; Or/and, in the first step, after adding metatitanic acid four butyl alcohol esters, with nitrogen by be adjusted to-40KPa of the pressure in reactor to-80KPa; Or/and, in second step, esterification is adjusted to normal pressure with nitrogen by the pressure in reactor after finishing; Or/and, in second step, after adding the composite titanium series catalysts in reactor, with nitrogen, the pressure in reactor is adjusted to normal pressure to-80KPa; Or/and, in second step, after adding carboxyl remover and sequestrant in reactor, with nitrogen, the pressure of the prepolymerization reaction in reactor is adjusted to 0.5 KPa to 2KPa; Or/and, in the 3rd step, after prepolymerization reaction completes, with nitrogen, the pressure of polycondensation in reactor is adjusted to 0Pa to 100Pa.

4. according to claim 1 or 2 or 3 described carboxy lower Biodegradable polyesters, it is characterized in that in the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of material in reactor is raised to 80 to 100 ℃; Or/and, in the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of charge in reactor is raised to 225 ℃ to 230 ℃ and carries out esterification.

5. according to claim 1 or 2 or 3 or 4 described carboxy lower Biodegradable polyesters, it is characterized in that in the first step being that under 30r/min to 100r/min condition, stirring 30min is even by mixing of materials in stir speed (S.S.); Or/and, in second step, after the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, in stir speed (S.S.), be under 30r/min to 100r/min condition, to stir after 15min mixes to add carboxyl remover and sequestrant.

6. the production method of a carboxy lower Biodegradable polyester, it is characterized in that raw materials by weight portion consists of 40 parts to 100 part 1, the 6-hexanodioic acid is or/and 1 part to 60 parts terephthalic acid and 80 parts to 100 part 1, the 4-butyleneglycol, wherein, the production method of this carboxy lower Biodegradable polyester obtains in the steps below: the first step, desired raw material is placed in to reactor, and the temperature of material in reactor is raised to 80 ℃ to 100 ℃, then mixing of materials is added to metatitanic acid four butyl alcohol esters of raw material weight 50ppm to 250ppm after evenly, at pressure, be then-40KPa is to-80KPa, temperature is 225 ℃ to 230 ℃, carry out esterification under the condition that stir speed (S.S.) is 50r/min to 100r/min, when the esterification water parts by weight of collecting reach 15 parts to 55 parts, stop esterification, second step, after esterification finishes, pressure in reactor is adjusted to normal pressure, then to the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, add the carboxyl remover of raw material weight 30ppm to 1000ppm and the sequestrant of raw material weight 10ppm to 300ppm after mixing, at pressure, be then that 0.5 KPa to 2KPa, temperature are to carry out prepolymerization reaction under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 10NM to 100NM, prepolymerization reaction completes, the 3rd step, after prepolymerization reaction completes, at pressure, be that 0Pa to 100Pa, temperature are to carry out polycondensation under 230 ℃ to 235 ℃, the stir speed (S.S.) condition that is 30r/min to 80r/min, when the stirring moment of torsion reaches 20NM to 80NM, stop polycondensation, after polycondensation finishes, use the nitrogen pressurization to get rid of the melt in reactor, with the cooling carboxy lower Biodegradable polyester that obtains of water-bath.

7. the production method of carboxy lower Biodegradable polyester according to claim 6, it is characterized in that the composite titanium series catalysts counts the organic titanic compound that comprises 50 parts to 98 parts by weight, the metal salt compound of the silicoorganic compound of 1 part to 50 parts and 1 part to 10 parts, wherein, organic titanic compound is metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, metatitanic acid four propyl alcohol esters, metatitanic acid four butyl alcohol esters, titanium isopropylate, metatitanic acid four isobutyl alcohol esters, metatitanic acid four trimethyl carbinol esters, metatitanic acid four isooctyl alcohol esters, metatitanic acid Fourth Ring hexanol ester, metatitanic acid four benzylalcohol esters, the cresols titanium, methyl ethyl diketone oxygen titanium, titanium ethylene glycolate, more than one in poly-metatitanic acid butyl alcohol ester etc., silicoorganic compound are trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, γ-aminopropyl methyldiethoxysilane, hexadecyl Trimethoxy silane, 3-aminopropyl triethoxysilane, vinyltriethoxysilane, methyl silicate, tetraethyl silicate, silicic acid propyl ester, butyl silicate, 1, more than one in two (trimethylsiloxy group) ethane of 2-, metal salt compound is more than one in lithium acetate, sodium acetate, lime acetate, cobaltous acetate, zinc acetate, manganous acetate, venus crystals, nickelous acetate, antimony acetate, acid chloride, lanthanum acetate, rubidium acetate, magnesium acetate, Magnesium Trisilicate, aluminum acetate, pure aluminium silicate, aluminium acetylacetonate, or/and, the carboxyl remover is Racemic glycidol, isopropyl glycidyl ether, n-butyl glycidyl ether, the n-octyl glycidyl ether, the dodecyl glycidyl ether, epoxy soybean oil, the cyclohexyl glycidyl ether, the benzyl glycidyl ether, furfuryl glycidyl ether, glycidyl allyl ether, glycidyl methacrylate, ethylene glycol diglycidylether, 1, the 4-butanediol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 2-cylohexanediol diglycidyl ether, 1, the 4-cylohexanediol diglycidyl ether, isocyanuric acid three-glycidyl ester, more than one in γ-glycidyl ether oxygen propyl trimethoxy silicane, or/and, inner complex is ethylene glycol, quadrol, butyleneglycol, 1, the 4-butanediamine, 2, the 2-dipyridyl, 2, 6-dicarboxyl pyridine, Dopamine HCL, α-amino isopropyl alcohol, diisopropanolamine (DIPA), tri-isopropanolamine, Diethylenetriaminee (DETA), triethylenetetramine, N, two (3-aminopropyl) quadrols of N'-, N-(2-hydroxyethyl) quadrol, N-acetyl quadrol, tetraacetyl ethylene diamine, N, the N-dimethyl-ethylenediamine, N, the N'-dimethyl-ethylenediamine, Tetramethyl Ethylene Diamine, N, the N'-diphenyl ethylene diamine, ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl-ethylenediamine-N, N', the N'-nitrilotriacetic, ethylene diamine tetra methylene phosphonic acid, polyvinyl alcohol, more than one in kollidon.

8. according to the production method of the described carboxy lower Biodegradable polyester of claim 6 or 7, it is characterized in that in the first step, after first reactor being replaced with nitrogen, then raw material is placed in to reactor; Or/and, in the first step, after adding metatitanic acid four butyl alcohol esters, with nitrogen by be adjusted to-40KPa of the pressure in reactor to-80KPa; Or/and, in second step, esterification is adjusted to normal pressure with nitrogen by the pressure in reactor after finishing; Or/and, in second step, after adding the composite titanium series catalysts in reactor, with nitrogen, the pressure in reactor is adjusted to normal pressure to-80KPa; Or/and, in second step, after adding carboxyl remover and sequestrant in reactor, with nitrogen, the pressure of the prepolymerization reaction in reactor is adjusted to 0.5 KPa to 2KPa; Or/and, in the 3rd step, after prepolymerization reaction completes, with nitrogen, the pressure of polycondensation in reactor is adjusted to 0Pa to 100Pa.

9. according to the production method of claim 6 or 7 or 8 described carboxy lower Biodegradable polyesters, it is characterized in that in the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of material in reactor is raised to 80 to 100 ℃; Or/and, in the first step, by 0.1 ℃/min to 1 ℃/min heat-up rate, the temperature of charge in reactor is raised to 225 ℃ to 230 ℃ and carries out esterification.

10. according to claim 6 or 7 or the production method of 8 or 9 described carboxy lower Biodegradable polyesters, it is characterized in that in the first step in stir speed (S.S.) being that to stir 30min under 30r/min to 100r/min condition even by mixing of materials; Or/and, in second step, after the composite titanium series catalysts that adds raw material weight 50ppm to 1000ppm in reactor, in stir speed (S.S.), be under 30r/min to 100r/min condition, to stir after 15min mixes to add carboxyl remover and sequestrant.