CN108129646A - A kind of polyester, the Preparation method and use of the high molecular weight of imido- - Google Patents
A kind of polyester, the Preparation method and use of the high molecular weight of imido- Download PDFInfo
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- CN108129646A CN108129646A CN201810078746.2A CN201810078746A CN108129646A CN 108129646 A CN108129646 A CN 108129646A CN 201810078746 A CN201810078746 A CN 201810078746A CN 108129646 A CN108129646 A CN 108129646A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
-
- 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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
- C08G63/87—Non-metals or inter-compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The present invention uses N (carboxymethyl) glycine, the dihydric alcohol with annular rigid group as monomer, using orgnometallic catalyst or sulphonic acids catalyst as esterification and polycondensation catalyst, by melt polymerization, obtain 160 ~ 190 DEG C of fusing point or softening point, number-average molecular weight 31000 ~ 46000 imido- high molecular weight polyester.The polyester of the high molecular weight of prepared imido- has the characteristics that higher-strength, and tensile strength is in 100 ~ 150MPa.The polyester of the high molecular weight of imido- disclosed by the invention, can be used as bottle grade PET use, and bottle grade material obtained is used to be valid up to the drink and food industry of 4 years as packaging material.After its completion is using function, it is discarded under natural soils environment, since second year, which starts obvious degradation under natural soils environment, the annual molecular weight and molecular weight 20 ~ 30% of the packaging material in the 2nd ~ 4 year.
Description
Technical field
The invention belongs to the synthesis fields of polyester product.Specifically, be a kind of polyester of the high molecular weight of imido-,
Preparation method and use.
Background technology
At 2013, China's plastics annual consumption became the big plastics country of consumption of the first in the world more than 60,000,000 tons.Tradition
Plastic products when bringing people's life convenient as its it is not degradable bring environmental problem, general plastics at least need
100 years ability natural degradations, the plastic products arbitrarily abandoned result in serious " white pollution " problem.Cause environmental problem
Waste plastic is mainly the discarding after the use of the staple commodities such as PE, PP, PS, and discarded polyester is also a part for white pollution
Source.The influence of environmental problem caused by avoid waste polyester, Recent study person are used for plastics industry in Devoting Major Efforts To Developing
Degradable poly ester material.Wherein, biology base is used for the polyester of Material synthesis to there is excellent degradation characteristic to become research heat
Point.It uses biology base that can also reduce dependence of the production of polyester to fossil resource for the polyester of Material synthesis simultaneously, has wide
Prospect.
But usual biology base polyester causes material intensity itself very weak due to itself being free of rigid radical, such as polylactic acid
（PLA）It is that one kind is based on renewable plant resources（Such as corn）Polyester material made of the starch raw material extracted has excellent
Degradation property, be widely used in polybag, film etc. packaging product in.But this type polyester material intensity of PLA
It is weaker, the plastic product of some strength is needed certain, such as plastic housing, plastic bottle, PLA is difficult to reach requirement.
There is reported in literature imines kind polyester that there is excellent degradation property（Jiang Z. Lipase-catalyzed
synthesis of poly(amine-co-esters) via copolymerization of diester with
amino-substituted diol.[J]. Biomacromolecules, 2010, 11(4):1089-93.）.But document carries
The imines drawn polyester intensity of the fatty long-chain gone out is too small, it is difficult to as plastic raw materials.Aromatic polyester is a kind of high intensity
Polyester material（Guolin Wu, Chengcai Pang, Jie Zhang, et al. Novel Vanillic Acid-
based Poly(ether-ester)s: From Synthesis to Properties[J]. Polymer Chemistry,
2015, 6(5):797-804.）.
In addition the dosage of conventional catalyst such as antimony oxide used in existing polyester preparation process is in reaction system
Large percentage, catalyst amount is big, catalysis it is of high cost, and coloured product lay particular stress on, content of beary metal it is higher, influence its beverage,
The industries such as food are used as high-grade packaging material.
Based on above-mentioned background, the present invention uses N- (carboxymethyl) glycine, the dihydric alcohol with annular rigid group as list
Body, using orgnometallic catalyst or sulphonic acids catalyst as esterification and polycondensation catalyst, by melt polymerization, obtain fusing point 160 ~
190 DEG C, number-average molecular weight 31000 ~ 46000 imido- high molecular weight polyester.Prepared process is using efficient
Metal is organic or sulphonic acids catalyst, catalyst amount is small, is catalyzed at low cost, polyester product pure color, tenor pole
It is low or without metal, and the polyester of the high molecular weight of synthesized imido- has the characteristics that higher-strength, tensile strength
In 100 ~ 150MPa.The polyester of the high molecular weight of imido- disclosed by the invention, can be in industries such as beverage, food as high-grade
Packaging material uses, and as bottle grade PET, bottle grade material obtained is used to be valid up to the drink and food industry conduct of 4 years
Packaging material.After its completion is using function, it is discarded under natural soils environment, since second year, which exists
Start to degrade under natural soils environment, the annual molecular weight and molecular weight 20 ~ 30% of the packaging material in the 2nd ~ 4 year.
Invention content
For the above problem of the prior art, the present invention uses N- (carboxymethyl) glycine, with annular rigid group
Dihydric alcohol synthesize a kind of excellent biology base polyester of performance for monomer, while the polyester has under natural soils environment
Excellent degradation property.
Purpose to realize the present invention, the present invention use following technical scheme：
A kind of polyester, the Preparation method and use of the high molecular weight of imido-, the polyester of the high molecular weight of the imido-
Structure is as follows：
The preparation method of the polyester of the high molecular weight of the imido- carries out as steps described below：
（1）N- (carboxymethyl) glycine and dihydric alcohol and catalyst are added in single-necked flask, nitrogen is replaced to anaerobic without watery
State carries out esterification 1 ~ 2 hour first under 130 ~ 150 DEG C of temperature, normal pressures, is then started to warm up from 150 DEG C, and 100 ~
1000Pa carries out polycondensation reaction, and heating rate is controlled at 20 DEG C/h, and 2h is finally reacted at 190 DEG C obtains imido-
The polyester crude product of high molecular weight.
（2）Polycondensation reaction terminates, and stops vacuumizing, and nitrogen is filled with to single-necked flask, after system is cooled to room temperature, Xiang Dan
Mouth flask adds in enough chloroform solvents, and polyester crude product is allowed fully to dissolve, and takes clear liquid after dissolving, and methanol solvate, which is added dropwise, to clear liquid is precipitated
Solid, centrifuging and taking solid wash the high molecular weight that solid, 80 DEG C of dryings obtain colourless imido- after 2 hours with ethyl alcohol
Polyester product.
Above-mentioned steps（1）In dihydric alcohol be catechol two（2- ethoxys）Ether, isophthalic two
Phenol two（2- ethoxys）Ether, 1,3- dihydroxy ethyl cyclohexane-ethers、
1,4- dihydroxy ethyl cyclohexane-ethersIn one kind or wherein two kinds of mixture.N-
The ratio between the molal quantity of (carboxymethyl) glycine and the total mole number of dihydric alcohol are 1:1.01~1:1.10.
Above-mentioned steps（1）In, catalyst used is orgnometallic catalyst or sulphonic acids catalyst.Wherein, metal has
Machine catalyst is zinc oxalate, antimony glycol, cyclopentadienyl titanium dichloride（C10H10Cl2Ti, CAS：1271-19-8）, bis cyclopentadienyl zirconium dichloride
（C10H10Cl2Zr, CAS：1291-32-3）, the luxuriant molybdenum of dichloro two（C10H10Cl2Mo, CAS：12184-22-4）, dichloro tungstocene
（C10H10Cl2W, CAS：12184-26-8 ）, dichloro hafnocene（C10H10Cl2Hf, CAS：：12116-66-4）, the luxuriant vanadium of dichloro two
（C10H10Cl2V, CAS：12083-48-6）, hydrogen chlorine zirconocene（C10H11ClZr, CAS:37342-97-5）In one kind；Sulphonic acids
Catalyst for pyrovinic acid, benzene sulfonic acid, sulfamic acid, p-methyl benzenesulfonic acid, p-chlorobenzenesulfonic acid, p-aminobenzene sulfonic acid, to methoxyl group
One kind in benzene sulfonic acid, p-nitrophenyl sulfonic acid.The ratio between the molal quantity of catalyst and the molal quantity of N- (carboxymethyl) glycine are
0.0001:1~0.001:1。
A kind of polyester, the Preparation method and use of the high molecular weight of imido-, the high molecular weight of the imido- are gathered
Application of the ester in the preparation of bottle grade PET material, method are as follows：It is fully kneaded by following components mass ratio, imido-
High molecular weight polyester: plasticizer: stabilizer 100:（30~45）∶（2~3）；Subsequent squeeze can be carried out after the completion of mixing
The molding process such as go out, be molded, stretching, being blow molded.The plasticizer is phthalic acid ester, tricresyl phosphate, sebacic acid
One kind of dibutyl ester；Stabilizer is triphenyl phosphate, one kind of trimethyl phosphate, phosphine acyl acetic acid three ethyl.
The present invention uses N- (carboxymethyl) glycine, the dihydric alcohol with annular rigid group as monomer, organic with metal
Catalyst or sulphonic acids catalyst are esterification and polycondensation catalyst, by melt polymerization, obtain 160 ~ 190 DEG C of fusing point, number is divided equally
Son amount is in the polyester of the high molecular weight of 31000 ~ 46000 colourless imido-s.
N- (carboxymethyl) glycine must be prepared：It can be by the glycine of low-cost biomass that derives from a wealth of sources, in water
Under conditions of solvent, alkalization is first passed through, then neutralize with monoxone reactant aqueous solution, sodium carbonate processing and acid and obtain monomer N-
(carboxymethyl) glycine.Therefore have the characteristics that cost of material is low, renewable, can effectively alleviate the money that polyester synthesis relies on oil
Source shortage problem；And another monomer of polyester synthesis can be condensed to come by catechol or resorcinol with chlorethanol,
These raw materials are cheap and easy to get.
The polyester preparation process of the high molecular weight of imido- of the present invention uses efficient metal organic or sulfonic acid
Class catalyst, catalyst amount is small, and catalysis is at low cost so that polyester product pure color, tenor are extremely low or without gold
Belong to, meet requirement of the packaging material of quality drinks and food service industry to raw material chromaticness；And the height of synthesized imido-
The polyester of molecular weight has the characteristics that higher-strength, and tensile strength is in 100 ~ 150MPa, and hot property is excellent, can be used as bottle grade and gathers
Prepared by ester raw material bottle grade material, can be used to be valid up to the drink and food industry of 4 years as packaging material.
Due to containing degradable imino group chain link in polyester construction, it is easy to degrade in natural soils environment.
It after its completion is using function, is discarded under natural soils environment, since second year, the packaging material is certainly
Start to degrade under right soil environment, the annual molecular weight and molecular weight 20 ~ 30% of the packaging material in the 2nd ~ 4 year.
The basic reason for having more than invention effect is：
1st, raw material well-chosen：N- (carboxymethyl) glycine cheap and easy to get is introduced in as monomer in polyester construction, complete
It is discarded into natural soil environment into its function, is easily degraded by natural sunlight, water, microbiological effect.And other one
Kind is with the neighbour of annular rigid group or resorcinol two（2- ethoxys）Ether or 1,3- dihydroxy ethyls cyclohexane-ether or 1,4- bis-
The introducing of ethoxy cyclohexane-ether can improve the mechanical property of polyester（Including tensile strength, stretch modulus, bending strength, bending
Modulus）, improve the hot property such as fusing point that it is used and be far above PLA, heat decomposition temperature greatly improves.
2nd, the Performance Match of catalyst and polyester synthetic process and raw material is optimal：Preparation process is had using efficient metal
Machine or sulphonic acids catalyst, catalyst amount is small, catalysis it is at low cost so that polyester product pure color, tenor it is extremely low or
Person is free of metal, meets requirement of the packaging material of quality drinks and food service industry to raw material chromaticness.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of D1 polyester made from the embodiment of the present invention 1.
Fig. 2 is that the GPC of D1 polyester made from the embodiment of the present invention 1 schemes.
Fig. 3 is that the TG of D1 polyester made from the embodiment of the present invention 1 schemes.
Fig. 4 degrades tendency chart for D1 polyester made from the embodiment of the present invention 1 under natural soils environment.
Specific embodiment
Example 1
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D1, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D1 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With resorcinol two（2- hydroxyls
Ethyl）Ether 3.962g, while cyclopentadienyl titanium dichloride is added in, it gradually heats up, the temperature for controlling reaction is 150 DEG C.4h-6h to be reacted
After, reaction system transparent and homogeneous, esterification is completed.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 190 DEG C, and reaction 2h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D1 after 80 DEG C of dryings.
Example 2
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D2, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D2 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With hydroquinone two（2- hydroxyls
Ethyl）Ether 3.962g, while 2.923mg (0.01mmol) bis cyclopentadienyl zirconium dichloride is added in, it gradually heats up, the temperature for controlling reaction is
150℃.After 4h-6h is reacted, reaction system transparent and homogeneous, esterification is completed.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 190 DEG C, and reaction 2h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D2 after 80 DEG C of dryings.
Example 3
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D3, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D3 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With 1,4- dihydroxy ethyl hexamethylenes
Alkane ether 2.549g, while 1.894mg (0.01mmol) zinc oxalate is added in, it gradually heats up, the temperature for controlling reaction is 160 DEG C.It treats
After reacting 4h-5h, reaction system transparent and homogeneous, esterification is completed.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D3 after 80 DEG C of dryings.
Example 4
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D4, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D4 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With 1,3- dihydroxy ethyl hexamethylenes
Alkane ether 2.549g, while 4.236mg (0.01mmol) antimony glycol is added in, it gradually heats up, the temperature for controlling reaction is 160 DEG C.
After 4h-5h is reacted, reaction system transparent and homogeneous, esterification is completed.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D4 after 80 DEG C of dryings.
Example 5
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D5, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D5 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With hydroquinone two（2- hydroxyls
Ethyl）Ether 1.981g and resorcinol two（2- ethoxys）Ether 1.981g, while 0.961mg (0.01mmol) methanesulfonic acid is added in,
It gradually heats up, the temperature for controlling reaction is 160 DEG C.After 4h-5h is reacted, reaction system transparent and homogeneous（Articulation point）, esterification
Reaction is completed.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D5 after 80 DEG C of dryings.
Example 6
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D6, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D6 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With hydroquinone two（2- hydroxyls
Ethyl）Ether 1.981g and 1,3- dihydroxy ethyl cyclohexane-ether 1.274g, while add in 1.732mg (0.01mmol) p-aminophenyl
Sulfonic acid gradually heats up, and the temperature for controlling reaction is 160 DEG C.After 4h-5h is reacted, reaction system transparent and homogeneous, esterification
It completes.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D6 after 80 DEG C of dryings.
Example 7
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D7, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D7 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With hydroquinone two（2- hydroxyls
Ethyl）Ether 1.981g and 1,4- dihydroxy ethyl cyclohexane-ether 1.274g, while 1.882mg (0.01mmol) is added in methoxybenzene
Sulfonic acid gradually heats up, and the temperature for controlling reaction is 160 DEG C.After 4h-5h is reacted, reaction system transparent and homogeneous, esterification
It completes.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D7 after 80 DEG C of dryings.
Example 8
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D8, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D8 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With resorcinol two（2- hydroxyls
Ethyl）Ether 1.981g and 1,3- dihydroxy ethyl cyclohexane-ether 1.274g, while add in 2.034mg (0.01mmol) p-nitrophenyl
Sulfonic acid gradually heats up, and the temperature for controlling reaction is 160 DEG C.After 4h-5h is reacted, reaction system transparent and homogeneous, esterification
It completes.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D8 after 80 DEG C of dryings.
Example 9
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D9, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D9 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With resorcinol two（2- hydroxyls
Ethyl）Ether 1.981g and 1,4- dihydroxy ethyl cyclohexane-ether 1.274g, while add in two cyclopentadienyl of 2.498mg (0.01mmol) hydrogen chlorine
Zirconium gradually heats up, and the temperature for controlling reaction is 160 DEG C.After 4h-5h is reacted, reaction system transparent and homogeneous, esterification is complete
Into.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D9 after 80 DEG C of dryings.
Example 10
Using N- (carboxymethyl) glycine as one of monomer synthesized degradable polyester D10, synthetic method.The polyester construction formula is：
The synthetic method of nitrogenous polyester D10 comprises the concrete steps that：
In single-necked flask after the drying, N- (carboxymethyl) glycine 2.662g is added in（20mmol）With 1,3- dihydroxy ethyl hexamethylenes
Alkane ether 1.274g and Isosorbide-5-Nitrae-dihydroxy ethyl cyclohexane-ether 1.274g, while 0.971mg (0.01mmol) sulfamic acid is added in, by
Step heating, the temperature for controlling reaction are 160 DEG C.After 4h-5h is reacted, reaction system transparent and homogeneous, esterification is completed.
After vacuumized nitrogen 3 times, start to warm up, it is slow after fast before heating rate, 150 ~ 190 DEG C/2 hours, while temperature
Degree control is 210 DEG C, and reaction 3h obtains polyester.It slowly vacuumizes again, until sticky polyester occurs, stirring stops.
Obtained polyester is dissolved in chloroformic solution, centrifugation takes clear liquid, instills in methanol solution, takes precipitation ethyl alcohol
Washing obtains D10 after 80 DEG C of dryings.
Polyester part of detecting experimental result is as shown in table 1 in example 1-10.
Table 1
M in table 1n1For the initial number-average molecular weight of sample, molecular weight distributions of the PDI for sample, T95%For 5% institute of sample heat resolve
The temperature needed, Mn2For the number-average molecular weight after degrading 3 years under sample natural soils environment.
* data source in：An aromatic plant metioned in ancient books in Shen, Sun Junquan, Wu Liangjiang wait rare earth coordinations catalyzing and synthesizing polylactic acid [J]
Acta Chim:sinica, 1990, 48(7):686-689.
* data sources in：Li Xiaomei, Zhou Wei, wangdan wait research [J] that plasticizer influence polylactic acid performance modern
Plastics processing and applications, 2008,20 (2):41-44.
Sample and PLA intensity contrasts are as shown in table 2 in example 1-3.
Table 2
* * data sources in：Zhang Wei, Liang Yurong, Wang Linyan wait the structure of the composite modified clay filling PLA composite materials of
With performance [J] plastics, 2017 (5):43-45.
Data comparison can obtain from table 1, the imido- high score that the present invention is synthesized using N- (carboxymethyl) glycine as one of monomer
The number-average molecular weight M of sub- weight polyestern1Than polylactic acid number-average molecular weight Mn1High 900 ~ 12300g/mol, imido- high molecular weight
Temperature T needed for the heat resolve 5% of polyester95%Than the temperature T needed for polylactic acid heat resolve 5%95%5 ~ 19 DEG C high, imido-
The fusing point or softening point of high molecular weight polyesters are 8.3 ~ 38.4 DEG C higher than the fusing point or softening point of polylactic acid.
Data comparison can obtain from table 2, the imido- that the present invention is synthesized using N- (carboxymethyl) glycine as one of monomer
The tensile strength of high molecular weight polyesters is higher 58.0 ~ 98.3MPa than the tensile strength of polylactic acid, the present invention is with the sweet ammonia of N- (carboxymethyl)
Acid is higher than the elongation at break of polylactic acid by 107.6 for the elongation at break of the imido- high molecular weight polyesters of one of monomer synthesis
~114.3%。
By data above it is found that the imido- macromolecule that the present invention is synthesized using N- (carboxymethyl) glycine as one of monomer
Compared with the polylactic acid of pure biology base, molecular weight, hot property, mechanical property etc. are obviously improved weight polyester.
The Mn1 and Mn2 comparisons from table 1 are it is found that the imido- height synthesized using N- (carboxymethyl) glycine as one of monomer
Molecular weight polyester is degraded under natural soils environment, and molecular weight of polyesters reduces half after 3 years, using N- (carboxymethyl) glycine as list
The imido- high molecular weight polyesters of one of body synthesis are suitable with the degradation property of PLA, and the fragrant adoption of existing literature report
Ester such as PET is that tens supreme a century is needed just to have notable degradation.
It is passed in conclusion having using N- (carboxymethyl) glycine as the imido- high molecular weight polyesters that one of monomer synthesizes
High molecular weight, high intensity, high-heat performance and the good mechanical property feature of system aromatic polyester PET, and have the poly- of biology base
Lactic acid feature degradable under natural soils environment, therefore the present patent application " a kind of polyester of the high molecular weight of imido-,
Preparation method and use " has good market prospects.
Although preferred embodiments of the present invention have been described, but those skilled in the art once know basic creation
Property concept, then additional changes and modifications may be made to these embodiments.So appended claims be intended to be construed to include it is excellent
It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these modification and variations
It is interior.
Claims (5)
1. a kind of polyester, the Preparation method and use of the high molecular weight of imido-, the polyester of the high molecular weight of the imido-
Structure it is as follows：
。
2. a kind of polyester of the high molecular weight of imido-, preparation method, the preparation of the polyester of the high molecular weight of the imido-
Method characteristic is to carry out as steps described below：
（1）N- (carboxymethyl) glycine and dihydric alcohol and catalyst are added in single-necked flask, nitrogen is replaced to anaerobic without watery
State carries out esterification 1 ~ 2 hour first under 130 ~ 150 DEG C of temperature, normal pressures, is then started to warm up from 150 DEG C, and 100 ~
1000Pa carries out polycondensation reaction, and heating rate is controlled at 20 DEG C/h, and 2h is finally reacted at 190 DEG C obtains imido-
The polyester crude product of high molecular weight.
（2）Polycondensation reaction terminates, and stops vacuumizing, and nitrogen is filled with to single-necked flask, after system is cooled to room temperature, is burnt to single port
Bottle adds in enough chloroform solvents, and polyester crude product is allowed fully to dissolve, and takes clear liquid after dissolving, and it is solid that methanol solvate precipitation is added dropwise to clear liquid
Body, centrifuging and taking solid wash the polyester product that solid, 80 DEG C of dryings obtain the high molecular weight of imido- after 2 hours with ethyl alcohol.
3. a kind of polyester of the high molecular weight of imido- according to claim 2, preparation method, it is characterised in that above-mentioned
Step（1）In dihydric alcohol be catechol two（2- ethoxys）Ether, resorcinol two（2- hydroxyls
Ethyl）Ether, 1,3- dihydroxy ethyl cyclohexane-ethers, 1,4- bis-
Ethoxy cyclohexane-etherIn one kind or wherein two kinds of mixture.N- (carboxymethyl)
The ratio between the molal quantity of glycine and the total mole number of dihydric alcohol are 1:1.01~1:1.10.
4. a kind of polyester of the high molecular weight of imido- according to claim 2, preparation method, it is characterised in that above-mentioned
Step（1）In, catalyst used is orgnometallic catalyst or sulphonic acids catalyst.Wherein, orgnometallic catalyst is grass
Sour zinc, antimony glycol, cyclopentadienyl titanium dichloride（C10H10Cl2Ti, CAS：1271-19-8）, bis cyclopentadienyl zirconium dichloride（C10H10Cl2Zr, CAS：
1291-32-3）, the luxuriant molybdenum of dichloro two（C10H10Cl2Mo, CAS：12184-22-4）, dichloro tungstocene（C10H10Cl2W, CAS：
12184-26-8 ）, dichloro hafnocene（C10H10Cl2Hf, CAS：：12116-66-4）, the luxuriant vanadium of dichloro two（C10H10Cl2V, CAS：
12083-48-6）, hydrogen chlorine zirconocene（C10H11ClZr, CAS:37342-97-5）In one kind；Sulphonic acids catalyst is methyl sulphur
Acid, benzene sulfonic acid, sulfamic acid, p-methyl benzenesulfonic acid, p-chlorobenzenesulfonic acid, p-aminobenzene sulfonic acid, to methoxy benzenesulfonic acid, p-nitrophenyl
One kind in sulfonic acid.The ratio between the molal quantity of catalyst and the molal quantity of N- (carboxymethyl) glycine are 0.0001:1~0.001:1.
5. a kind of polyester, the Preparation method and use of the high molecular weight of imido-, the polyester of the high molecular weight of the imido-
Application in the preparation of bottle grade PET material, it is characterised in that：It is fully kneaded by following components mass ratio, imido-
High molecular weight polyester: plasticizer: stabilizer 100:（30~45）∶（2~3）；Subsequent squeeze can be carried out after the completion of mixing
The molding process such as go out, be molded, stretching, being blow molded.The plasticizer is phthalic acid ester, tricresyl phosphate, sebacic acid
One kind of dibutyl ester；Stabilizer is triphenyl phosphate, one kind of trimethyl phosphate, phosphine acyl acetic acid three ethyl.
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| JP2001151877A (en) * | 1999-11-29 | 2001-06-05 | Toray Ind Inc | Polyester composition and film composed of the same |
| WO2003074583A1 (en) * | 2002-03-06 | 2003-09-12 | Unilever Plc | Azetidinium-functionalised polymers and compositions containing the same |
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| CN101412804A (en) * | 2008-11-23 | 2009-04-22 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN107226902A (en) * | 2017-06-02 | 2017-10-03 | 武汉科技大学 | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof |
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|---|---|---|---|---|
| US6824766B2 (en) * | 1998-04-17 | 2004-11-30 | Enzon, Inc. | Biodegradable high molecular weight polymeric linkers and their conjugates |
| JP2001151877A (en) * | 1999-11-29 | 2001-06-05 | Toray Ind Inc | Polyester composition and film composed of the same |
| WO2003074583A1 (en) * | 2002-03-06 | 2003-09-12 | Unilever Plc | Azetidinium-functionalised polymers and compositions containing the same |
| US20050227010A1 (en) * | 2002-03-06 | 2005-10-13 | Parker Andrew P | Azetidinium-functionalised polymers and compositions containing the same |
| CN101412804A (en) * | 2008-11-23 | 2009-04-22 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN107226902A (en) * | 2017-06-02 | 2017-10-03 | 武汉科技大学 | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof |
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