CN109575263A - Low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester preparation method - Google Patents
Low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester preparation method Download PDFInfo
- Publication number
- CN109575263A CN109575263A CN201710904460.0A CN201710904460A CN109575263A CN 109575263 A CN109575263 A CN 109575263A CN 201710904460 A CN201710904460 A CN 201710904460A CN 109575263 A CN109575263 A CN 109575263A
- Authority
- CN
- China
- Prior art keywords
- succinic
- adipic acid
- acid
- butanediol ester
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08G63/78—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester, mainly solve the problems, such as that poly-succinic -co- adipic acid-butanediol ester content of carboxyl end group existing in the prior art is higher.The present invention by using a kind of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester preparation method, it is characterised in that before esterification starts or esterification terminates that glycol composition is added before finishing reaction starts；Wherein, the glycol composition is selected from the technical solution of trimethylolpropane and other at least one polyalcohols, preferably solves the problems, such as this, can be used in the preparation of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester.
Description
Technical field
The present invention relates to a kind of preparation methods of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester.
Background technique
Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate (PBT) etc. are weights
The synthetic material wanted, it is widely used due to can be applied to the fields such as synthetic fibers, engineering plastics with a variety of excellent performances.
But these polymer can not degrade in nature, bring white pollution is the great difficult problem in the puzzlement whole world.To solve
White pollution is endangered to environment bring, and the exploitation of degradation material is the trend of future development, the use ratio of degradation material
Example will be growing day by day.
The poly-succinic -co- adipic acid-butanediol ester being copolymerized by succinic acid, adipic acid and 1,4- butanediol
It (PBSA) is the PBS base resin with outstanding degradation capability, degradation capability is higher than PBS, while easy processing forms, and is degradable thin
The main product of membrane material is widely used in the fields such as packaging film, the plated film of paper, medical supplies, foamed material, agricultural mulching,
Overseas market demand is huge.
In preparing poly-succinic -co- adipic acid-butanediol ester, since butanediol easily decomposes at high temperature, tetrahydro is generated
The by-product of furans and water, therefore the polymer for preparing the catalyst acquisition high molecular weight of aromatic polyester cannot be used.
Preparing catalyst used in the polymer being copolymerized as succinic acid, adipic acid and butanediol in the prior art is alkoxy
Titanium, alkoxy tin, germanium oxide etc., as patent CN101910245, CN1088945, CN1923872, CN101434689,
Butyl titanate disclosed in JP2004018674A2, tetraisopropyl titanate, Dibutyltin oxide, tin oxide, stannous chloride, germanium
Compound etc..
Titanium series catalyst is not present problem of environmental pollution, is particularly suitable for aliphatic since its activity is high, is free of heavy metal
The industrialized production of polyester.It is used to prepare the catalysis of poly-succinic -co- adipic acid-butanediol ester titanate ester in the prior art
There is facile hydrolysis, chance water can generate the defect of insoluble precipitating for agent, causes catalyst activity to reduce, contains to polymer end carboxyl
Amount has an adverse effect.Content of carboxyl end group height is unfavorable for the heat resistance and processing performance of polymer, is unfavorable in storing process
Stability.Chinese patent CN103772683A solves the problems, such as that titanium compound dissolves each other with butanediol, but do not refer to prepare it is low
Content of carboxyl end group poly-succinic -co- adipic acid-butanediol ester method.
Summary of the invention
The technical problem to be solved by the present invention is to poly-succinic -co- adipic acid-butanediol esters existing in the prior art
The higher problem of content of carboxyl end group provides a kind of new low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester system
Preparation Method.This method has the advantages that poly-succinic -co- adipic acid-butanediol ester content of carboxyl end group can be effectively reduced.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of low terminal carboxy content poly-succinic-
The preparation method of co- adipic acid-butanediol ester, before esterification starts or esterification terminates to add before finishing reaction starts
Enter glycol composition；
Wherein, the glycol composition is selected from trimethylolpropane and other at least one polyalcohols.
In above-mentioned technical proposal, the glycol composition is trimethylolpropane and other at least one polyhydric alcohol conjugates
It forms, other described polyalcohols are selected from C3~C6One kind of polyalcohol, further preferably from pentaerythrite, neopentyl glycol, sorb
At least one of alcohol, glycerol, xylitol or mannitol.
In above-mentioned technical proposal, the weight ratio of trimethylolpropane and other polyalcohols is preferred in the glycol composition
For 1:(1~15), further preferably the weight ratio of trimethylolpropane and other polyalcohols is 1:(1~8).
In above-mentioned technical proposal, the preparation method preferably includes following steps: being with succinic acid, adipic acid, butanediol
Raw material uses liquid condition titanium series catalyst in reaction temperature for 150~230 DEG C, reaction pressure be normal pressure~0.5MPa under the conditions of into
Row esterification obtains esterification products, is then 230~250 DEG C in reaction temperature, reaction pressure is less than the vacuum item of 120Pa
Under part carry out polycondensation reaction obtain poly-succinic -co- adipic acid-butanediol ester, used in liquid condition titanium series catalyst include
The reaction product of following raw material:
(A) with the titanium compound of following general formula:
Ti(OR)4
R is the alkyl selected from 1~10 carbon atom；
(B) selected from the dihydric alcohol with 2~10 carbon atoms；
(C) selected from least one of organic acid aliphatic organic acid；
(D) in the periodic table of elements IA at least one metallic compound；
Before esterification starts or esterification terminates that the glycol composition is added before finishing reaction starts；
Wherein, the molar ratio of the dihydric alcohol (B) and titanium compound (A) are (1~20): 1, aliphatic organic acid (C) with
The molar ratio of titanium compound (A) is (1~10): 1, the molar ratio of metallic compound (D) and titanium compound (A) are (0~10): and 1,
Weight polyester ratio is 0.01%~0.4% to the glycol composition together.
In above-mentioned technical proposal, further preferably: the molar ratio of the dihydric alcohol (B) and titanium compound (A) be (1~
10): 1, the molar ratio of aliphatic organic acid (C) and titanium compound (A) are (1~5): 1, metallic compound (D) and titanium compound
(A) molar ratio is (2~6): 1, weight polyester ratio is 0.03%~0.3% to the glycol composition together.Based on generation
Poly-succinic -co- adipic acid-butanediol ester weight, the additive amount of catalyst is calculated as 50~120mg/kg with titanium atom.
In above-mentioned technical proposal, the preferred embodiment of titanium compound (A) is selected from tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid four
At least one of propyl ester, tetraisopropyl titanate or butyl titanate.The preferred embodiment of dihydric alcohol (B) is selected from ethylene glycol, 1,3-
At least one of propylene glycol, 1,4- butanediol, 1,6-HD, 1,4 cyclohexane dimethanol.Aliphatic organic acid (C) it is excellent
Scheme is selected to be selected from least one of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid or lactic acid.Aliphatic organic acid (C)
It is anhydride or crystalline hydrate.The preferred embodiment of IA race metallic compound (D) is selected from least one of lithium, sodium or potassium.
The preparation method of liquid condition titanium series catalyst in the present invention the following steps are included:
A) by titanium compound, to react 0.5~25 under the conditions of 20~250 DEG C small with the dihydric alcohol containing 2~10 carbon atoms
When, wherein titanium compound is Ti (OR)4, R is the alkyl selected from 1~10 carbon atom, and white depositions are precipitated, and will be produced after reaction
Object separation, and it is washed with distilled water residue, product is dried in vacuo, white powder substance is obtained；
B) in the white powder substance that above-mentioned a) step obtains, aliphatic organic acid, IA race metallic compound is added,
Reaction temperature is 30~250 DEG C, the reaction time 0.5~25 hour, obtains can be used for producing poly-succinic -co- adipic acid-fourth two
The liquid condition titanium series catalyst of alcohol ester.
Addition trimethylolpropane and composition made of at least one polyhydric alcohol conjugate in the present invention, increase end hydroxyl
Base blocks probability, reduces copolyesters content of carboxyl end group, and be not introduced into the functional group not included in copolymer molecule chain, not shadow
Ring the green environmental protection of copolymer.
The preparation method of low and middle-end carboxyl-content poly-succinic -co- adipic acid-butanediol ester of the present invention:
Known preparation process of polyester can be used, esterification, reaction temperature are carried out by succinic acid, adipic acid and butanediol
Degree is 150~230 DEG C, and reaction pressure is normal pressure~0.5MPa.Then polycondensation reaction is carried out under vacuum conditions, and reaction temperature is
230~250 DEG C, reaction pressure is less than 120Pa.Liquid condition titanium series catalyst is added in reaction system after completion of the esterification reaction,
Dosage is 50~120mg/kg (being based on polycondensation product quality).The polyalcohol of trimethylolpropane and at least one polyhydric alcohol conjugate
Composition can be added before esterification starts, and can also terminate to be added before finishing reaction starts in esterification.Polycondensation
Cast Strip, pelletizing after reaction, obtain polymeric articles.
In the present invention, low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester inherent viscosity and carboxyl end group
Content is tested by the following method:
A) inherent viscosity: phenol tetrachloroethane mixed liquor makees solvent, is measured at a temperature of 25 DEG C with dark type viscometer.
B) content of carboxyl end group: content of carboxyl end group X is calculated as follows, and unit is mole (mol/t) per ton.
X=(V-V0)×c×103/m
In formula:
V: the numerical value of potassium hydroxide-ethanol standard titration solution volume consumed by sample solution, unit are milliliter (mL)；
V0: the numerical value of potassium hydroxide-ethanol standard titration solution volume, unit are milliliter consumed by blank solution
(mL)；
C: the concentration of potassium hydroxide-ethanol standard titration solution, unit are mole every liter (mol/L)；
M: the sample weighting amount of sample, unit are gram (g).
Using technical solution of the present invention, by using addition trimethylolpropane and other at least one polyhydric alcohol conjugates
Made of glycol composition, be Ti (OR) with general formula4Titanium compound, dihydric alcohol, aliphatic organic acid and IA race metallization
The product that reacts of object is closed as liquid condition titanium series catalyst, poly-succinic -co- adipic acid-butanediol ester obtained with compared with
Low content of carboxyl end group, is smaller than 10mol/t；Achieve preferable technical effect.
The present invention will be further described below by way of examples.
Specific embodiment
[comparative example 1]
The preparation of liquid condition titanium series catalyst A
It in the reactor equipped with blender, condenser and thermometer, is added 18.6 grams of ethylene glycol (0.3 mole), toward instead
It answers and is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions are precipitated, are reacted 2 hours at 80 DEG C, it will
Product centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder object
Matter.White powder substance after drying is placed in the reactor equipped with blender, condenser and thermometer, lactic acid 27 is added
Gram (0.3 mole), 18 grams of butanediol (0.2 mole) react 3 hours at 100 DEG C, obtain light yellow transparent liquid, are catalyst
A。
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 280 grams of succinic acid, 87 g of adipic acid and 348 grams of butanediols, mixing is made into slurry, is added in polymeric kettle, into
Row esterification, esterification temperature are 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.It is added and urges after esterification
Agent A (polymer quality based on generation, the weight of titanium atom are 50mg/kg) is vacuumized and is decompressed to system pressure and is lower than
100Pa, simultaneous reactions temperature gradually rise to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop it is anti-
It answers, later continuously squeezes out reaction product from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 1.63dL/g, end
Carboxyl-content is 29mol/t.
[embodiment 1]
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 280 grams of succinic acid, 87 g of adipic acid and 348 grams of butanediols, mixing is made into slurry, is added in polymeric kettle, into
Row esterification, esterification temperature are 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.It is added and urges after esterification
Agent A (polymer quality based on generation, the weight of titanium atom are 50mg/kg), trimethylolpropane and pentaerythrite (weight
Than the composition (composition together weight polyester ratio be 0.03%) for 1:1), vacuumizes and is decompressed to system pressure lower than 100Pa,
Simultaneous reactions temperature gradually rises to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop reaction, later
Reaction product is continuously squeezed out from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 1.96dL/g, and carboxyl end group contains
Amount is 12mol/t.
[comparative example 2]
The preparation of liquid condition titanium series catalyst B
It in the reactor equipped with blender, condenser and thermometer, is added 18.6 grams of ethylene glycol (0.3 mole), toward instead
It answers and is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions are precipitated, are reacted 2 hours at 100 DEG C,
Product is centrifugated, and is washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder
Substance.White powder substance after drying is placed in the reactor equipped with blender, condenser and thermometer, lactic acid is added
18 grams (0.2 mole), 96 gram 25% of sodium hydrate aqueous solution (0.6 mole), 27 grams of butanediol (0.3 mole) is at 120 DEG C
Reaction 4 hours, obtains colourless transparent liquid, is catalyst B.
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 280 grams of succinic acid, 87 g of adipic acid and 348 grams of butanediols, mixing is made into slurry, is added in polymeric kettle, into
Row esterification, esterification temperature are 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.It is added and urges after esterification
Agent B (polymer quality based on generation, the weight of titanium atom are 70mg/kg) is vacuumized and is decompressed to system pressure and is lower than
100Pa, simultaneous reactions temperature gradually rise to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop it is anti-
It answers, later continuously squeezes out reaction product from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 1.84dL/g, end
Carboxyl-content is 30mol/t.
[embodiment 2]
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 280 grams of succinic acid, 87 g of adipic acid, 348 grams of butanediols, trimethylolpropane and neopentyl glycol, (weight ratio is
Composition (weight polyester ratio is 0.08% to composition together) 1:5), mixing is made into slurry, is added in polymeric kettle, carries out ester
Change reaction, esterification temperature is 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.Catalyst is added after esterification
B (polymer quality based on generation, the weight of titanium atom are 70mg/kg) is vacuumized and is decompressed to system pressure lower than 100Pa,
Simultaneous reactions temperature gradually rises to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop reaction, later
Reaction product is continuously squeezed out from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 1.98dL/g, and carboxyl end group contains
Amount is 9mol/t.
[comparative example 3]
The preparation of liquid condition titanium series catalyst C
It in the reactor equipped with blender, condenser and thermometer, is added 37.2 grams of ethylene glycol (0.6 mole), toward instead
It answers and is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions are precipitated, are reacted 2 hours at 70 DEG C, it will
Product centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder object
Matter.White powder substance after drying is placed in the reactor equipped with blender, condenser and thermometer, a water lemon is added
42 grams (0.2 moles) of lemon acid, 48 gram 25% of sodium hydrate aqueous solution (0.3 mole), 54 grams of butanediol (0.6 mole) are at 90 DEG C
Lower reaction 4 hours, obtains colourless transparent liquid, is catalyst C.
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 245 grams of succinic acid, 130 g of adipic acid and 374 grams of butanediols, mixing is made into slurry, is added in polymeric kettle, into
Row esterification, esterification temperature are 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.It is added and urges after esterification
Agent C (polymer quality based on generation, the weight of titanium atom are 120mg/kg) is vacuumized and is decompressed to system pressure and is lower than
100Pa, simultaneous reactions temperature gradually rise to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop it is anti-
It answers, later continuously squeezes out reaction product from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 2.01dL/g, end
Carboxyl-content is 35mol/t.
[embodiment 3]
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 245 grams of succinic acid, 130 g of adipic acid, 374 grams of butanediols, trimethylolpropane and mannitol (weight ratio 1:
8) composition (weight polyester ratio is 0.3% to composition together), mixing is made into slurry, is added in polymeric kettle, is esterified
Reaction, esterification temperature are 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.Catalyst C is added after esterification
(polymer quality based on generation, the weight of titanium atom are 120mg/kg) vacuumizes and is decompressed to system pressure lower than 100Pa,
Simultaneous reactions temperature gradually rises to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop reaction, later
Reaction product is continuously squeezed out from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 2.17dL/g, and carboxyl end group contains
Amount is 8mol/t.
[comparative example 4]
The preparation of liquid condition titanium series catalyst D
It in the reactor equipped with blender, condenser and thermometer, is added 24.8 grams of ethylene glycol (0.4 mole), toward instead
It answers and is slowly dropped into device 28.4 grams of tetraisopropyl titanate (0.1 mole), white depositions are precipitated, are reacted 2 hours at 70 DEG C, it will
Product centrifuge separation, and be washed with distilled water residue 3 times, product is dried in vacuo at 70 DEG C, obtains white powder object
Matter.White powder substance after drying is placed in the reactor equipped with blender, condenser and thermometer, a water lemon is added
105 grams (0.5 moles) of lemon acid, 32 gram 25% of sodium hydrate aqueous solution (0.2 mole), 54 grams of butanediol (0.6 mole) are 100
It is reacted 3 hours at DEG C, obtains colourless transparent liquid, be catalyst D.
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 245 grams of succinic acid, 130 g of adipic acid and 400 grams of butanediols, mixing is made into slurry, is added in polymeric kettle, into
Row esterification, esterification temperature are 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.It is added and urges after esterification
Agent D (polymer quality based on generation, the weight of titanium atom are 100mg/kg) is vacuumized and is decompressed to system pressure and is lower than
100Pa, simultaneous reactions temperature gradually rise to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop it is anti-
It answers, later continuously squeezes out reaction product from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 1.86dL/g, end
Carboxyl-content is 33mol/t.
[comparative example 5]
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 245 grams of succinic acid, 130 g of adipic acid, 400 grams of butanediols and sorbierite, (weight polyester ratio is sorbierite together
0.25%), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 160~200 DEG C, passes through essence
The water that distillation unit discharge reaction generates.Catalyst D (polymer quality based on generation, the weight of titanium atom are added after esterification
Amount is 100mg/kg), it vacuumizes and is decompressed to system pressure lower than 100Pa, simultaneous reactions temperature gradually rises to 240 DEG C, starts
Polycondensation reaction, when reacted between reach 180 minutes after stop reaction, reaction product is continuously squeezed from polymeric kettle bottom Cast Strip later
Out, cooling, pelletizing, measurement inherent viscosity are 1.84dL/g, content of carboxyl end group 31mol/t.
[embodiment 4]
The preparation of poly-succinic -co- adipic acid-butanediol ester
By 245 grams of succinic acid, 130 g of adipic acid, 400 grams of butanediols, trimethylolpropane and sorbierite (weight ratio 1:
4) composition (weight polyester ratio is 0.25% to composition together), mixing is made into slurry, is added in polymeric kettle, is esterified
Reaction, esterification temperature are 160~200 DEG C, and the water that reaction generates is discharged by rectifier unit.Catalyst D is added after esterification
(polymer quality based on generation, the weight of titanium atom are 100mg/kg) vacuumizes and is decompressed to system pressure lower than 100Pa,
Simultaneous reactions temperature gradually rises to 240 DEG C, start polycondensation reaction, when reacted between reach 180 minutes after stop reaction, later
Reaction product is continuously squeezed out from polymeric kettle bottom Cast Strip, cooling, pelletizing, measurement inherent viscosity is 2.23dL/g, and carboxyl end group contains
Amount is 10mol/t.
Claims (10)
1. a kind of preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester, it is characterised in that be esterified
Before reaction starts or esterification terminates that glycol composition is added before finishing reaction starts；
Wherein, the glycol composition is selected from trimethylolpropane and other at least one polyalcohols.
2. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 1,
It is characterized in that other polyalcohols are selected from C3~C6One of polyalcohol.
3. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 1,
It is characterized in that at least one of other polyalcohols in pentaerythrite, neopentyl glycol, sorbierite, glycerol, xylitol or mannitol
Kind.
4. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 1,
The weight ratio for being characterized in that trimethylolpropane and other polyalcohols is 1:(1~15).
5. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 1,
The weight ratio for being characterized in that trimethylolpropane and other polyalcohols is 1:(1~8).
6. any low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester preparation according to claim 1~5
Method, it is characterised in that include the following steps using succinic acid, adipic acid, butanediol as raw material, using liquid condition titanium series catalyst in
Reaction temperature is 150~230 DEG C, and reaction pressure carries out esterification under the conditions of being normal pressure~0.5MPa, obtains esterification products, so
It is afterwards 230~250 DEG C in reaction temperature, reaction pressure carries out polycondensation reaction and obtains polybutadiene under the vacuum condition less than 120Pa
Sour -co- adipic acid-butanediol ester, used in liquid condition titanium series catalyst include following raw material reaction product:
(A) with the titanium compound of following general formula:
Ti(OR)4
R is the alkyl selected from 1~10 carbon atom；
(B) selected from the dihydric alcohol with 2~10 carbon atoms；
(C) selected from least one of organic acid aliphatic organic acid；
(D) in the periodic table of elements IA at least one metallic compound；
Before esterification starts or esterification terminates that the glycol composition is added before finishing reaction starts；
Wherein, the molar ratio of the dihydric alcohol (B) and titanium compound (A) are (1~20): 1, aliphatic organic acid (C) and titanizing
The molar ratio for closing object (A) is (1~10): 1, the molar ratio of metallic compound (D) and titanium compound (A) are (0~10): and 1, it is polynary
Weight polyester ratio is 0.01%~0.4% to alcohol composition together.
7. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 6,
The molar ratio for being characterized in that the dihydric alcohol (B) and titanium compound (A) is (1~10): 1, aliphatic organic acid (C) and titanizing are closed
The molar ratio of object (A) is (1~5): 1, the molar ratio of metallic compound (D) and titanium compound (A) are (2~6): 1.
8. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 6,
It is characterized in that weight polyester ratio is 0.03%~0.3% to the glycol composition together.
9. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 6,
It is characterized in that the reaction product titanium compound (A) of liquid condition titanium series catalyst is selected from tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid 4 third
At least one of ester, tetraisopropyl titanate or butyl titanate；Dihydric alcohol (B) is selected from ethylene glycol, 1,3- propylene glycol, 1,4- fourth
At least one of glycol, 1,6-HD, 1,4 cyclohexane dimethanol；Aliphatic organic acid (C) is selected from citric acid, apple
At least one of acid, tartaric acid, oxalic acid, succinic acid or lactic acid；IA race metallic compound (D) in lithium, sodium or potassium extremely
Few one kind.
10. the preparation method of low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester according to claim 6,
It is characterized in that poly-succinic -co- adipic acid-butanediol ester weight based on generation, the additive amount of catalyst is with titanium atom
It is calculated as 50~120mg/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710904460.0A CN109575263B (en) | 2017-09-29 | 2017-09-29 | Preparation method of poly (butylene succinate-co-adipate-glycol) with low carboxyl end group content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710904460.0A CN109575263B (en) | 2017-09-29 | 2017-09-29 | Preparation method of poly (butylene succinate-co-adipate-glycol) with low carboxyl end group content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109575263A true CN109575263A (en) | 2019-04-05 |
| CN109575263B CN109575263B (en) | 2021-05-11 |
Family
ID=65913942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710904460.0A Active CN109575263B (en) | 2017-09-29 | 2017-09-29 | Preparation method of poly (butylene succinate-co-adipate-glycol) with low carboxyl end group content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109575263B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229439A (en) * | 2019-06-20 | 2019-09-13 | 江苏爱特恩高分子材料有限公司 | A kind of novel polyvinyl-chloride use helps rapidoprint and preparation method thereof |
| CN112542296A (en) * | 2020-12-04 | 2021-03-23 | 刚和石油(营口)有限公司 | Biodegradable high-ignition-point insulating fluid |
| CN114075324A (en) * | 2020-08-20 | 2022-02-22 | 南亚塑胶工业股份有限公司 | Method for producing polyester polyol |
| CN114835884A (en) * | 2022-04-11 | 2022-08-02 | 四川轻化工大学 | Poly (butylene succinate) and preparation method thereof |
| CN115044023A (en) * | 2022-07-15 | 2022-09-13 | 四川轻化工大学 | Blocked PBS (poly (butylene succinate)) and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55127421A (en) * | 1979-03-27 | 1980-10-02 | Matsushita Electric Works Ltd | Preparation of polyester resin molding material |
| US20050233179A1 (en) * | 2004-04-14 | 2005-10-20 | Fuji Photo Film Co., Ltd. | Magnetic recording medium |
| CN101716524A (en) * | 2009-12-08 | 2010-06-02 | 金发科技股份有限公司 | High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis |
| CN103408739A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of butyleneadipate-terephthalate with low terminal carboxyl group content |
| CN105585702A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Polyester used for plates and preparing method thereof |
| CN106866945A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | For the liquid condition titanium series catalyst of poly-succinic -co- adipic acid-butanediol ester |
| CN106867207A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The production method of low colour poly-succinic -co- adipic acid-butanediol ester |
-
2017
- 2017-09-29 CN CN201710904460.0A patent/CN109575263B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55127421A (en) * | 1979-03-27 | 1980-10-02 | Matsushita Electric Works Ltd | Preparation of polyester resin molding material |
| US20050233179A1 (en) * | 2004-04-14 | 2005-10-20 | Fuji Photo Film Co., Ltd. | Magnetic recording medium |
| CN101716524A (en) * | 2009-12-08 | 2010-06-02 | 金发科技股份有限公司 | High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis |
| CN103408739A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of butyleneadipate-terephthalate with low terminal carboxyl group content |
| CN105585702A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Polyester used for plates and preparing method thereof |
| CN106866945A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | For the liquid condition titanium series catalyst of poly-succinic -co- adipic acid-butanediol ester |
| CN106867207A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The production method of low colour poly-succinic -co- adipic acid-butanediol ester |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229439A (en) * | 2019-06-20 | 2019-09-13 | 江苏爱特恩高分子材料有限公司 | A kind of novel polyvinyl-chloride use helps rapidoprint and preparation method thereof |
| CN114075324A (en) * | 2020-08-20 | 2022-02-22 | 南亚塑胶工业股份有限公司 | Method for producing polyester polyol |
| CN114075324B (en) * | 2020-08-20 | 2024-02-20 | 南亚塑胶工业股份有限公司 | Process for producing polyester polyol |
| CN112542296A (en) * | 2020-12-04 | 2021-03-23 | 刚和石油(营口)有限公司 | Biodegradable high-ignition-point insulating fluid |
| CN112542296B (en) * | 2020-12-04 | 2021-10-29 | 刚和石油(营口)有限公司 | Biodegradable high-ignition-point insulating fluid |
| CN114835884A (en) * | 2022-04-11 | 2022-08-02 | 四川轻化工大学 | Poly (butylene succinate) and preparation method thereof |
| CN115044023A (en) * | 2022-07-15 | 2022-09-13 | 四川轻化工大学 | Blocked PBS (poly (butylene succinate)) and preparation method thereof |
| CN115044023B (en) * | 2022-07-15 | 2023-08-29 | 四川轻化工大学 | Blocked PBS and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109575263B (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109575263A (en) | Low terminal carboxy content poly-succinic -co- adipic acid-butanediol ester preparation method | |
| EP2894182B1 (en) | Method for continuously preparing biodegradable aliphatic/aromatic polyester copolymer | |
| EP2751163B1 (en) | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst | |
| CN104558574B (en) | Titanium series polyester catalyst | |
| CN101942078A (en) | Titanium polyester catalyst for preparing polyester | |
| CN103539928B (en) | Titanium series polyester catalyst and the method for producing semi-dull polyester | |
| TWI636073B (en) | Method for the production of a titanium containing catalyst, titanium containing catalyst, method for the production of polyester and polyester | |
| CN101323661B (en) | Process for producing polyester | |
| CN101121777B (en) | Titanium series polyester catalyst | |
| CN106866945A (en) | For the liquid condition titanium series catalyst of poly-succinic -co- adipic acid-butanediol ester | |
| CN111269405A (en) | Preparation method of bio-based polyester for inhibiting discoloration | |
| TWI806052B (en) | Polyester composition | |
| CN101121778A (en) | Method for preparing titanium series catalyst | |
| CN102718948B (en) | Method for preparing aliphatic polyoxalate | |
| CN102453238B (en) | Preparation method of biodegradable polyester | |
| CN102140165A (en) | Biodegradable copolyester and preparation method thereof | |
| CN106867207B (en) | The production method of low color value poly-succinic -co- adipic acid-butanediol ester | |
| CN101148499B (en) | Titanium series catalyst | |
| CN104163913A (en) | Preparation method of polybutylece aliphatic diacid terephthalate type copolyester | |
| CN104558554B (en) | The preparation method of polyester resin | |
| CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
| CN103739834B (en) | The production method of solid phase titanium polyester | |
| CN115403749A (en) | Degradable poly (butylene adipate/terephthalate-co-glycollic acid) copolyester and preparation method thereof | |
| CN101173038B (en) | Method for producing polyester | |
| CN103342802A (en) | Preparation method of polybutylene terephthalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |