CN109666133A - A kind of linear randomly biodegradable copolymer ester and preparation method - Google Patents
A kind of linear randomly biodegradable copolymer ester and preparation method Download PDFInfo
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- CN109666133A CN109666133A CN201710967223.9A CN201710967223A CN109666133A CN 109666133 A CN109666133 A CN 109666133A CN 201710967223 A CN201710967223 A CN 201710967223A CN 109666133 A CN109666133 A CN 109666133A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The present invention relates to polymeric material fields, disclose a kind of linear randomly biodegradable copolymer ester and preparation method.The copolyesters has aliphatic ester structural unit and aromatic ester structural unit, the melt index that the copolyesters uses ISO 1133-2005 method to measure under 150 DEG C, 2.16kg load is 3.0-5.5g/10min, and the melt index for using ISO 1133-2005 method to measure under 190 DEG C, 2.16kg load is 10-20g/10min.Copolyesters of the present invention has lower melt index, and molecular weight with higher, tensile mechanical properties are preferable.
Description
Technical field
The present invention relates to polymeric material fields, more particularly to a kind of linear random biodegradable copolymer ester and system
Preparation Method.
Background technique
Be now widely used for industry and daily life in thermoplastic aromatic polyester have excellent heat stability can and
Mechanical property, it is easy to process, it is cheap.For example, polyethylene terephthalate (PET) and polybutylene terephthalate
Ester (PBT), is widely used in the manufacture of fiber, film and container.However, these aromatic polyesters are difficult to after use is discarded
Degradation, microorganism is also not observed so far has any apparent directly degradation to aromatic polyester such as PET, PBT.In order to combine
The excellent performance of aromatic polyester, since the 1980s, those skilled in the art are dedicated to synthctic fat-aromatic copolyester
The research of ester, i.e., introduce aromatic segments in aliphatic polyester, both ensure that the copolyesters has the Optimality of aromatic polyester
Can, in turn ensure the biodegradable of the copolyesters.For example, by aliphatic dibasic acid or derivatives thereof, aliphatic dihydroxy alcohol,
Aromatic acid or derivatives thereof can prepare biodegradable aliphatic-aromatic copolyester.The copolyesters is with moral
The production of BASF AG, stateTo represent, raw material 1,6- adipic acid (AA), 1,4-butanediol (BDO), to benzene two
Formic acid dimethyl ester (DMT), production technology are as follows: esterification occurs for AA and BDO, and ester exchange reaction occurs for DMT and BDO, then
Esterification products and transesterification product is set to carry out copolycondensation together.
Chinese patent application CN1807485A is disclosed by aromatic acid or carboxylate, aliphatic dihydroxy alcohol, fat
The system of race's binary acid or derivatives thereof prepares linear random fat/aromatic copolyesters, joined rare earth catalyst in preparation process
System, fat/aromatic copolyesters molecular weight with higher of preparation.However, with the development of processed and applied, this linear nothing
Rule fat/aromatic copolyesters also expose some performance deficiencies, for example melt index is higher, are difficult to meet the need of processing aspect
It asks, therefore under the premise of not changing product structure, the biodegradable copolymer ester for preparing low melt index becomes to have very much must
It wants.
Summary of the invention
The purpose of the invention is to overcome the melt index of the Biodegradable Copolyester of existing method preparation is higher to lack
It falls into, a kind of linear randomly biodegradable copolymer ester and preparation method is provided.
To achieve the goals above, one aspect of the present invention provides a kind of linear random biodegradable copolymer ester, this is total
Polyester has aromatic ester structural unit shown in aliphatic ester structural unit shown in formula (1) and formula (2),
Wherein, R1' and R3' identical or different, and it is each independently selected from alkylidene；R2' selected from by alkylidene and cycloalkylidene
The group of composition；R4' it is arlydene；The copolyesters is measured under 150 DEG C, 2.16kg load using ISO 1133-2005 method
Melt index be 3-5.5g/10min, under 190 DEG C, 2.16kg load using ISO 1133-2005 method measurement melting
Index is 10-20g/10min.
The present invention also provides a kind of preparation methods of linear random biodegradable copolymer ester, this method comprises:
(1) component a and component b are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates, starts to vacuumize, and precondensation is first carried out under the first low vacuum, then under the first high vacuum
Polycondensation reaction is carried out, polymer P 1 is made, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum
Power；
(2) component b and component c are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates；
(3) polymer P 1 prepared by step (1) is mixed with reaction product prepared by step (2) and carries out polycondensation reaction；
Wherein, the component a is aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, cycloaliphatic diacid and alicyclic
At least one of acid anhydrides of binary acid；The component b is aliphatic dihydroxy alcohol；The component c is aromatic acid and virtue
At least one of the acid anhydrides of fragrant race's binary acid；
First catalyst is oxide, M (OR selected from M1)nWith M (- OOCR2)nAt least one of compound or
Their mixture, wherein M is titanium, antimony or zinc, and n is the valence state of M, R1For C1-C10Alkyl, R2For C1-C30Alkyl；
Second catalyst is at least one organo-tin compound；
The third catalyst is that at least one chemical formula is RE (R3)3Compound, wherein RE is thulium,
R3For selected from halogen, alkoxy, aryloxy group, levulinic ketone group and R4At least one of COO- group, R4For C1-C30Alkyl.
The present invention also provides the linear random biodegradable copolymer esters prepared by the above method.
The linear random biodegradable copolymer ester prepared according to the method described in the present invention has lower melt index,
Physical and mechanical property is excellent, can satisfy the demand of processing aspect.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Linear random biodegradable copolymer ester of the present invention have aliphatic ester structural unit shown in formula (1) and
Aromatic ester structural unit shown in formula (2).
In formula (1) and (2), R1' and R3' identical or different, and it is each independently selected from alkylidene, such as can be C2-
The alkylidene of C10.The alkylidene of the C2-C10 can be straight-chain alkyl-sub or the alkylidene with branch.Under preferable case,
R1' and R3' it is each independently selected from the alkylidene of C2-C8, the more preferably alkylidene of C2-C6.
In formula (1) and (2), R2' selected from the group being made of alkylidene and cycloalkylidene, such as can be the Asia of C1-C12
The cycloalkylidene of alkyl or C3-C12.The alkylidene of the C1-C12 can be straight-chain alkyl-sub or the alkylidene with branch.
Under preferable case, R2' the alkylidene for being C1-C8, the more preferably alkylidene of C2-C6.
In formula (1) and (2), R4' it is arlydene, the preferably arlydene of C6-C12.The arlydene can for
The group of at least one phenyl ring, naphthalene nucleus and anthracene nucleus.Under preferable case, R4' it is following arlydene:
Wherein, R5、R6、R7、R8、R9And R10It is each independently hydrogen, C1-C4Alkyl, F, Cl ,-NO2,-CN or-OR11,
Wherein, R11For C1-C4Alkyl.
In the present invention, the linear random biodegradable copolymer ester uses ISO under 150 DEG C, 2.16kg load
The melt index of 1133-2005 method measurement is 3-5.5g/10min, specifically, such as can be 3g/10min, 3.5g/
10min、4g/10min、4.5g/10min、4.6g/10min、4.7g/10min、4.8g/10min、4.9g/10min、5.0g/
In 10min, 5.1g/10min, 5.2g/10min, 5.3g/10min, 5.4g/10min, 5.5g/10min and these point values
The arbitrary value in range that any two are constituted.
In the present invention, the linear random biodegradable copolymer ester uses ISO under 190 DEG C, 2.16kg load
The melt index of 1133-2005 method measurement is 10-20g/10min, specifically, such as can be 10g/10min, 11g/
10min、12g/10min、13g/10min、13.5g/10min、14g/10min、14.5g/10min、15g/10min、15.5g/
10min、16g/10min、16.5g/10min、17g/10min、17.5g/10min、18g/10min、18.5g/10min、19g/
The arbitrary value in range that any two in 10min, 19.5g/10min, 20g/10min and these point values are constituted.
In the present invention, the number-average molecular weight of the linear random biodegradable copolymer ester can be 50,000-7.5 ten thousand, excellent
It is selected as 5.2 ten thousand -7.3 ten thousand.In the present invention, the number-average molecular weight of polymer is measured according to gel permeation chromatography (GPC) method.
In the present invention, the weight average molecular weight of the linear random biodegradable copolymer ester can be 10.5 ten thousand -15 ten thousand,
Preferably 10.7 ten thousand -13 ten thousand.In the present invention, the weight average molecular weight of polymer is measured according to gel permeation chromatography (GPC) method.
In the present invention, the elongation at break of the linear random biodegradable copolymer ester can be 500-2200%,
Preferably 700-2100%.In the present invention, the elongation at break of copolyesters is measured according to the method for ASTM D638-03.
In the present invention, the fracture tensile strength of the linear random biodegradable copolymer ester can be 8-35MPa, excellent
It is selected as 10-32MPa.In the present invention, the fracture tensile strength of copolyesters is measured according to the method for ASTM D638-03.
In the present invention, the glass transition temperature of the linear random biodegradable copolymer ester can be for -32 DEG C extremely
30℃.In the present invention, the glass transition temperature of copolyesters is measured according to differential scanning calorimeter (DSC) measuring method.
It is of the present invention that linearly randomly the preparation method of biodegradable copolymer ester includes:
(1) component a and component b are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates, starts to vacuumize, and precondensation is first carried out under the first low vacuum, then under the first high vacuum
Polycondensation reaction is carried out, polymer P 1 is made, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum
Power；
(2) component b and component c are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates；
(3) polymer P 1 prepared by step (1) is mixed with reaction product prepared by step (2) and carries out polycondensation reaction.
In method of the present invention, the component a is aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, alicyclic ring
At least one of race's binary acid and the acid anhydrides of cycloaliphatic diacid.The chemical general formula of the aliphatic dibasic acid can be
HOOC-R13- COOH, wherein R13It can be the alkylidene of C1-C12, and the alkylidene of the C1-C12 can be straight chained alkyl
Or the alkylidene with branch.Under preferable case, R13It is C3-C10 for the alkylidene of C1-C8 namely the aliphatic dibasic acid
Aliphatic dibasic acid, the more preferably aliphatic dibasic acid of C3-C7.The cycloaliphatic diacid can be for at least one
The binary acid of cycloaliphatic ring.Under preferable case, the cycloaliphatic diacid is the cycloaliphatic diacid of C5-C10.
In method of the present invention, the component b is aliphatic dihydroxy alcohol, the preferably binary aliphatic of C2-C6
Alcohol.The chemical general formula of the aliphatic dihydroxy alcohol can be HO-R12- OH, wherein R12It can be C2-10Alkylidene, and R12It can
Think straight chained alkyl or the alkyl with branch.Under preferable case, the component b be selected from ethylene glycol, propylene glycol, butanediol,
At least one of pentanediol, hexylene glycol, heptandiol and ethohexadiol.
In method of the present invention, the component c is in the acid anhydrides of aromatic acid and aromatic acid
It is at least one.The chemical general formula of the aromatic acid can be HOOC-Ar-COOH, wherein Ar can be for at least one
The group of a phenyl ring, naphthalene nucleus and anthracene nucleus, under preferable case, Ar is following aryl:
Wherein, R5、R6、R7、R8、R9And R10It is each independently hydrogen, C1-C4Alkyl, F, Cl ,-NO2,-CN or-OR11,
Wherein, R11For C1-C4Alkyl.
A preferred embodiment of the invention, the component a are selected from C3-C10Aliphatic dibasic acid, C3-C10
Aliphatic dibasic acid acid anhydrides, C5-C10Cycloaliphatic diacid and C5-C10Cycloaliphatic diacid acid anhydrides at least one
Kind；The component b is 1,4- butanediol；The component c is terephthalic acid (TPA) and/or terephthalic anhydride.According to the preferred reality
Linear random biodegradable copolymer ester molecular weight with higher and good tensile mechanical properties prepared by the mode of applying.
In method of the present invention, first catalyst is oxide, M (OR selected from M1)nWith M (- OOCR2)n
At least one of compound or their mixture, wherein M be titanium, antimony or zinc, n be M valence state, R1For C1-C10Alkane
Base, R2For C1-C30Alkyl.In order to make the Biodegradable polyester finally prepared that there is the molecular weight that further increases and smaller
Molecular weight distribution index, while improving the tensile mechanical properties of Biodegradable polyester finally prepared, first catalysis
Agent is preferably selected from the oxide and titanyl compound of alkoxytitanium, antimony acetate, zinc acetate, the oxide of zinc, antimony at least
It is a kind of.In further preferred situation, first catalyst is selected from butyl titanate (Ti (OC4H9)4), titanium isopropoxide, two
At least one of titanium oxide, antimony oxide, antimony acetate and zinc acetate.
In method of the present invention, second catalyst is at least one organo-tin compound.It is final in order to make
The Biodegradable polyester of preparation has the molecular weight and lesser molecular weight distribution index further increased, while improving final
The tensile mechanical properties of the Biodegradable polyester of preparation, second catalyst are preferably selected from Dibutyltin oxide, oxidation
Aminomethyl phenyl tin, tetraethyl tin, oxidation Hexaethyl tin, oxidation six cyclohexyl, two tin, oxidation two (dodecyl) tin, triethyl group hydroxyl
Ji Xi, fentin hydroxide, acetic acid triisobutyl tin, dibutyltin diacetate, tin dilaurate stannous phenide, monobutyl tri-chlorination
In tin, tributyltin chloride, dibutyltin sulfide, butylhydroxy tin oxide, methane stannonic acid, ethyl stannonic acid and butyl stannonic acid extremely
Few one kind.In further preferred situation, second catalyst is selected from Dibutyltin oxide, tetraethyl tin, triphenyl hydroxyl
Tin, dibutyltin diacetate, tin dilaurate stannous phenide, monobutyl-tin-trichloride, tributyltin chloride, dibutyltin sulfide,
At least two mixture in butylhydroxy tin oxide, methane stannonic acid, ethyl stannonic acid and butyl stannonic acid.In this case,
The content of each component of the third catalyst can be 10-90 moles of %, preferably 30-70 moles of %.
In method of the present invention, the third catalyst is that at least one chemical formula is RE (R3)3Compound,
Wherein, RE is thulium, R3For selected from halogen, alkoxy, aryloxy group, levulinic ketone group and R4In COO- group extremely
Few one kind, R4For C1-C30Alkyl.In order to make the Biodegradable polyester finally prepared have the molecular weight that further increases and
Lesser molecular weight distribution index, while improving the tensile mechanical properties of Biodegradable polyester finally prepared, described the
It is RE (R in chemical formula in three catalyst3)3Compound in, RE is preferably lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium or scandium；Institute
Stating halogen is chlorine or bromine, and the alkoxy is C3-C6Alkoxy, the aryloxy group be include at least one phenyl ring and/or naphthalene nucleus
Aryloxy group, R4For C1-C20Alkyl.In further preferred situation, RE is selected from lanthanum, cerium, praseodymium, neodymium or scandium, and the halogen is
Chlorine or bromine, the alkyl in the alkoxy are isopropyl, normal-butyl or isopentyl, and the aryl in the aryloxy group is 2,6-, bis- uncle
Butyl -4- aminomethyl phenyl or 4- butyl phenyl, R4For C3-C18Alkyl.In preferred situation, the third catalyst is second
Acyl acetone lanthanum, acetylacetone,2,4-pentanedione neodymium, isopropoxy neodymium, isopropoxy lanthanum, isopropoxy scandium, Lanthanum Stearate, stearic acid neodymium, chlorination
Lanthanum, three (2,6- di-t-butyl -4- methylphenoxy) one of lanthanums and their hydrate or a variety of.
In method of the present invention, the esterification condition in step (1) can be in conventional esterification condition
It properly selects.Under preferable case, the esterification reaction temperature is 180-220 DEG C.In the esterification reaction process, work as reaction
When the water of generation is greater than the 98% of theoretical production quantity, it can be determined that terminate for esterification.
In method of the present invention, in step (1), it is preferable that the absolute pressure under the first low vacuum is than first
Absolute pressure high 300-600Pa, more preferable 400-500Pa under high vacuum.Absolute pressure under preferable case, under the first low vacuum
Power is 500-600Pa, and the absolute pressure under the first high vacuum is 200Pa or less (such as 10-200Pa).
In method of the present invention, in step (1), the reaction condition of the precondensation may include: that temperature is
240-260 DEG C, the time is 0.5-2 hours.
In method of the present invention, in step (1), the reaction condition of the polycondensation may include: that temperature is
250-270 DEG C, the time is 2-3 hours.
In method of the present invention, in step (1), the component a and the molar ratio of the dosage of the component b are
1:0.8-6 preferably 1:0.8-3.
In method of the present invention, the esterification condition in step (2) can be in conventional esterification condition
It properly selects.Under preferable case, the esterification reaction temperature is 150-200 DEG C.In the esterification reaction process, work as reaction
When the water of generation is greater than the 98% of theoretical production quantity, it can be determined that terminate for esterification.
In method of the present invention, in step (2), the component c and the molar ratio of the dosage of the component b are
1:0.8-6 preferably 1:0.8-3.
In method of the present invention, in step (3), it is preferable that the polycondensation process includes: to make mixture
Material (i.e. the mixture of polymer P 1 and the reaction product of step (2) preparation) first carries out precondensation under the second low vacuum, then
Polycondensation is carried out under the second high vacuum, wherein the absolute pressure under the second low vacuum is greater than the absolute pressure under the second high vacuum.
In method of the present invention, it is preferable that the absolute pressure under the second low vacuum is than exhausted under the second high vacuum
300-600Pa high to pressure, more preferable 400-500Pa.Under preferable case, the absolute pressure under the second low vacuum is 500-
600Pa, the absolute pressure under the second high vacuum are 200Pa or less (such as 10-200Pa).
In method of the present invention, in step (3), the reaction condition of the precondensation may include: that temperature is
240-260 DEG C, the time is 0.5-2 hours.
In method of the present invention, in step (3), the reaction condition of the polycondensation may include: that temperature is
250-270 DEG C, the time is 2-3 hours.
A preferred embodiment of the invention, the preparation method packet of the linear random biodegradable copolymer ester
It includes:
(1) component a and component b are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction；The component a is aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, cycloaliphatic diacid and cycloaliphatic diacid
At least one of acid anhydrides；The component b is aliphatic dihydroxy alcohol；The molar ratio of the additional amount of the additional amount and component b of component a
Start to vacuumize until esterification terminates for 1:0.8-6, preferably 1:0.8-3, first in low vacuum (vacuum degree 500-
600Pa), precondensation is carried out at 240-260 DEG C, then carry out high vacuum (vacuum degree is less than 200Pa) polycondensation reaction, reaction temperature
It is 250-270 DEG C, reacts 2-3 hours, reaction was completed, and polymer P 1 is made, optionally carries out crushing pelletizing.
(2) in the presence of the first catalyst, the second catalyst and third catalyst, it is esterified component b and component c
Reaction, the component c are at least one of aromatic acid and/or the acid anhydrides of aromatic acid；The additional amount of component c
Molar ratio with the additional amount of component b is 1:0.8-6；Terminate to esterification.
(3) polymer P 1 is added in the reaction product of step (2) preparation, carries out polycondensation reaction, first preshrunk together
It is poly-, then carry out final polycondensation reaction 2-3 hours, until reaction terminates.
In method of the present invention, above-mentioned steps (1) and step (2), can be with any one elder generations without successive point
Carry out after another, can also both carry out simultaneously.
The present invention also provides the linear random biodegradable copolymer esters prepared by the above method.The copolyesters has
Lower melt index, specifically, the copolyesters are measured under 150 DEG C, 2.16kg load using ISO 1133-2005 method
Melt index be 3-5.5g/10min, under 190 DEG C, 2.16kg load using ISO 1133-2005 method measurement melting
Index is 10-20g/10min.
The invention will be further described by the following examples, but protection scope of the present invention is not limited only to this.
In the following Examples and Comparative Examples, Lanthanum Stearate is made according to the method for embodiment A5 in CN1807485A.
Embodiment 1
The metatitanic acid of the 1,4- succinic acid of 202.6g, the 1,4- butanediol of 200g, 0.245g are added into the reaction kettle of 2.5L
Four butyl esters (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) of 0.1g, 0.14g triphen
Base hydroxyl tin (being purchased from Beijing chemical reagents corporation) and the Lanthanum Stearate of 0.31g are heated with stirring to reflux in a nitrogen atmosphere,
The temperature was then adjusted to 220 DEG C, when the water wait react generation is greater than the 98% of theoretical production quantity, by the absolute pressure tune in reaction kettle
Section is to 550Pa, and temperature of reaction kettle is 255 DEG C, carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, and temperature is adjusted
Yellow polymer P11 is obtained to terminal within polycondensation 2 hours to 260 DEG C, and at this temperature and pressure.
The metatitanic acid four of the terephthalic acid (TPA) of 285g, the 1,4- butanediol of 200g, 0.245g are added into the reaction kettle of 2.5L
The tristearin of Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) and 0.31g of butyl ester (being purchased from Beijing chemical reagents corporation), 0.2g
Sour lanthanum, in a nitrogen atmosphere, heating stirring is to flowing back, and the temperature was then adjusted to 200 DEG C, the water of generation to be reacted is greater than theoretical generate
Amount 98% when, the polymer P 11 is added, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle 255
DEG C, it carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and at this temperature and pressure
Obtain light yellow copolymer SP1 to terminal within polycondensation 2 hours.
Comparative example 1
The metatitanic acid four of the terephthalic acid (TPA) of 285g, the 1,4- butanediol of 200g, 0.245g are added into the reaction kettle of 2.5L
Butyl ester (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from company, Beijing Chemical Factory No. 3) of 0.1g and 0.14g
Fentin hydroxide (is purchased from Beijing chemical reagents corporation), in a nitrogen atmosphere, is heated with stirring to reflux, the temperature was then adjusted to
220 DEG C, when the water wait react generation is greater than the 98% of theoretical production quantity, be added thereto 202.6g 1, 4- succinic acid, 200
The Lanthanum Stearate of 1,4-butanediol and 0.62g continues heating stirring to reflux, the temperature was then adjusted to 200 DEG C, generation to be reacted
When water steams completely, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is 255 DEG C, and it is small to carry out precondensation 1
When, continue for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and polycondensation 7 hours at this temperature and pressure, obtains shallow
Yellow copolymer DP1.
Embodiment 2
Four fourth of metatitanic acid of the 1,4- succinic acid of 269g, the 1,4- butanediol of 266g, 0.3g is added into the reaction kettle of 2.5L
The stearic acid of Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) and 0.4g of ester (being purchased from Beijing chemical reagents corporation), 0.13g
Lanthanum is heated with stirring to reflux in a nitrogen atmosphere, and the temperature was then adjusted to 220 DEG C, the water of generation to be reacted is greater than theoretical production quantity
98% when, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is 255 DEG C, carry out precondensation 1 hour, after
Continuous that vacuum degree is adjusted to 150Pa, temperature is adjusted to 260 DEG C, and obtains to terminal within polycondensation 3 hours at this temperature and pressure
Yellow polymer P21.
The metatitanic acid four of the terephthalic acid (TPA) of 204g, the 1,4- butanediol of 144g, 0.174g are added into the reaction kettle of 2.5L
Butyl ester (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) of 0.071g, 0.099g three
The Lanthanum Stearate of phenyl hydroxyl tin (being purchased from Beijing chemical reagents corporation) and 0.22g, in a nitrogen atmosphere, heating stirring is extremely returned
When the water wait react generation is greater than the 98% of theoretical production quantity, the polymer P 21 is added the temperature was then adjusted to 200 DEG C in stream,
Absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is 255 DEG C, carries out precondensation 1 hour, continues vacuum
Degree is adjusted to 150Pa, and temperature is adjusted to 260 DEG C, and obtains light yellow total to terminal within polycondensation 3 hours at this temperature and pressure
Polymers SP2.
Comparative example 2
The metatitanic acid four of the terephthalic acid (TPA) of 204g, the 1,4- butanediol of 144g, 0.174g are added into the reaction kettle of 2.5L
The Dibutyltin oxide (being purchased from company, Beijing Chemical Factory No. 3) and 0.099g of butyl ester (being purchased from Beijing chemical reagents corporation), 0.071g
Fentin hydroxide (be purchased from Beijing chemical reagents corporation), in a nitrogen atmosphere, be heated with stirring to reflux, the temperature was then adjusted to
220 DEG C, when the water wait react generation is greater than the 98% of theoretical production quantity, the 1, 4- succinic acid of 269g, 266g are added thereto
The Lanthanum Stearate of 1,4-butanediol and 0.62g continues heating stirring to reflux, the temperature was then adjusted to 200 DEG C, generation to be reacted
When water steams completely, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is 255 DEG C, and it is small to carry out precondensation 1
When, continue for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and polycondensation 7 hours at this temperature and pressure, obtains shallow
Yellow copolymer DP2.
Embodiment 3
The metatitanic acid of the 1,4- succinic acid of 82.8g, the 1,4- butanediol of 76.0g, 0.245g are added into the reaction kettle of 2.5L
Four butyl esters (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) of 0.1g, 0.14g triphen
Base hydroxyl tin (being purchased from Beijing chemical reagents corporation) and the Lanthanum Stearate of 0.31g are heated with stirring to reflux in a nitrogen atmosphere,
The temperature was then adjusted to 200 DEG C, when the water wait react generation is greater than the 98% of theoretical production quantity, by the absolute pressure tune in reaction kettle
Section is to 600Pa, and temperature of reaction kettle is 255 DEG C, carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 100Pa, and temperature is adjusted
Yellow polymer P31 is obtained to terminal within polycondensation 2 hours to 260 DEG C, and at this temperature and pressure.
The metatitanic acid four of the terephthalic acid (TPA) of 466g, the 1,4- butanediol of 303g, 0.245g are added into the reaction kettle of 2.5L
The tristearin of Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) and 0.31g of butyl ester (being purchased from Beijing chemical reagents corporation), 0.2g
Sour lanthanum, in a nitrogen atmosphere, heating stirring is to flowing back, and the temperature was then adjusted to 200 DEG C, the water of generation to be reacted is greater than theoretical generate
Amount 98% when, the polymer P 11 is added, the absolute pressure in reaction kettle is adjusted to 600Pa, temperature of reaction kettle 255
DEG C, it carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and at this temperature and pressure
Obtain light yellow copolymer SP3 to terminal within polycondensation 2 hours.
Test case
The number-average molecular weight of copolymer SP1-SP3 and DP1-DP2 are detected according to gel permeation chromatography (GPC) method and are again divided equally
Son amount；
The molecular weight distribution index of copolymer is detected and calculated according to GPC method；
The glass transition temperature of copolymer is detected according to differential scanning calorimeter (DSC) measuring method；
The tensile mechanical properties of copolymer SP1-SP3 and DP1-DP2 are detected as being broken according to the method for ASTM D638-03
Elongation and fracture tensile strength；
The measurement of melt index: using American science instrument manufacturing company CS-127 type fusion index instrument measurement copolymer
Melt flow rate (MFR) (MI), under 190 DEG C of (or 150 DEG C), 2.16kg loads, using " the thermoplastic of ISO 1133-2005
The measurement of melt mass flow rate and melt volume-flow rate " standard is measured.
Its testing result is as shown in table 1 below.
Table 1
The copolyesters prepared according to the method described in the present invention it can be seen from the data of upper table 1 has lower melting
Index, and molecular weight with higher, tensile mechanical properties are preferable.
Claims (11)
1. a kind of linear random biodegradable copolymer ester, the copolyesters have aliphatic ester structural unit shown in formula (1) and
Aromatic ester structural unit shown in formula (2),
Wherein, R1' and R3' identical or different, and it is each independently selected from alkylidene；R2' selected from being made of alkylidene and cycloalkylidene
Group；R4' it is arlydene；
The melt index that the copolyesters uses ISO 1133-2005 method to measure under 150 DEG C, 2.16kg load is 3-
5.5g/10min, the melt index for using ISO 1133-2005 method to measure under 190 DEG C, 2.16kg load is 10-20g/
10min。
2. copolyesters according to claim 1, wherein R1' and R3' identical, and it is selected from the alkylidene of C2-C6；R2' it is C2-
The alkylidene of C6；R4' the arlydene for being C6-C12.
3. a kind of preparation method of linear random biodegradable copolymer ester, this method comprises:
(1) component a and component b is made to carry out esterification in the presence of the first catalyst, the second catalyst and third catalyst,
Terminate to esterification, start to vacuumize, first carries out precondensation under the first low vacuum, then contract under the first high vacuum
Poly- reaction, is made polymer P 1, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum；
(2) component b and component c is made to carry out esterification in the presence of the first catalyst, the second catalyst and third catalyst,
Terminate to esterification；
(3) polymer P 1 prepared by step (1) is mixed with reaction product prepared by step (2) and carries out polycondensation reaction；
Wherein, the component a is aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, cycloaliphatic diacid and alicyclic binary
At least one of the acid anhydrides of acid；The component b is aliphatic dihydroxy alcohol；The component c is aromatic acid and aromatic series
At least one of acid anhydrides of binary acid；
First catalyst is oxide, M (OR selected from M1)nWith M (- OOCR2)nAt least one of compound or they
Mixture, wherein M is titanium, antimony or zinc, and n is the valence state of M, R1For C1-C10Alkyl, R2For C1-C30Alkyl；
Second catalyst is at least one organo-tin compound；
The third catalyst is that at least one chemical formula is RE (R3)3Compound, wherein RE is thulium, R3For
Selected from halogen, alkoxy, aryloxy group, levulinic ketone group and R4At least one of COO- group, R4For C1-C30Alkyl.
4. according to the method described in claim 3, wherein, the esterification reaction temperature in step (1) is 180-220 DEG C, step (2)
In esterification reaction temperature be 150-200 DEG C.
5. according to the method described in claim 3, wherein, in step (1), the absolute pressure under the first low vacuum is 500-
600Pa, the absolute pressure under the first high vacuum are 200Pa or less.
6. the method according to claim 3 or 5, wherein in step (1), the reaction condition of the precondensation includes: temperature
Degree is 240-260 DEG C, and the time is 0.5-2 hours；The reaction condition of the polycondensation includes: that temperature is 250-270 DEG C, time 2-
3 hours.
7. the method according to any one of claim 3-5, wherein in step (3), the polycondensation process packet
It includes: so that mixed material is first carried out precondensation under the second low vacuum, polycondensation is then carried out under the second high vacuum, wherein second
Absolute pressure under low vacuum is greater than the absolute pressure under the second high vacuum.
8. according to the method described in claim 7, wherein, the absolute pressure under the second low vacuum is 500-600Pa, the second Gao Zhen
Absolute pressure under empty is 200Pa or less.
9. according to the method described in claim 7, wherein, in step (3), the reaction condition of the precondensation includes: temperature
It is 240-260 DEG C, the time is 0.5-2 hours；The reaction condition of the polycondensation includes: that temperature is 250-270 DEG C, time 2-3
Hour.
10. the method according to any one of claim 3-9, wherein the component a is the binary aliphatic of C3-C7
At least one of the acid anhydrides of aliphatic dibasic acid of acid and C3-C7；The component b is the aliphatic dihydroxy alcohol of C2-C6；It is described
Component c is at least one of aromatic acid and acid anhydrides of aromatic acid of C8-C14 of C8-C14.
11. the linear random biodegradable copolymer ester of the preparation of the method as described in any one of claim 3-10.
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| US20100249355A1 (en) * | 2007-11-20 | 2010-09-30 | Davis Mark B | Methods for making polyolefins |
| CN102453237A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of biodegradable polyester |
| CN102838735A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100249355A1 (en) * | 2007-11-20 | 2010-09-30 | Davis Mark B | Methods for making polyolefins |
| CN102453237A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of biodegradable polyester |
| CN102838735A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
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