CN108047436B - A kind of poly butylene succinate chain extension method - Google Patents
A kind of poly butylene succinate chain extension method Download PDFInfo
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- CN108047436B CN108047436B CN201711377219.3A CN201711377219A CN108047436B CN 108047436 B CN108047436 B CN 108047436B CN 201711377219 A CN201711377219 A CN 201711377219A CN 108047436 B CN108047436 B CN 108047436B
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- -1 poly butylene succinate chain Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 36
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 36
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 28
- 239000004970 Chain extender Substances 0.000 claims description 21
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 18
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 18
- 229960002703 undecylenic acid Drugs 0.000 claims description 18
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- FSYNWQTYZZDUEN-UHFFFAOYSA-N anisole;2-hydroxy-1,2-diphenylethanone Chemical group COC1=CC=CC=C1.C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 FSYNWQTYZZDUEN-UHFFFAOYSA-N 0.000 claims description 8
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 claims description 6
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- PGTWZHXOSWQKCY-UHFFFAOYSA-N 1,8-Octanedithiol Chemical compound SCCCCCCCCS PGTWZHXOSWQKCY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical group SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000001678 irradiating effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000011173 large scale experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of chain extension method of poly butylene succinate, its main feature is that using sulfydryl-alkene reaction in click chemistry, by the terminal-modified polyester for obtaining double bond sealing end of the poly butylene succinate of terminal hydroxy group.After being dissolved in chloroform, dimercaptan and photoinitiator is added, the poly butylene succinate of high molecular weight can be obtained after a certain period of time through ultraviolet light.The method of the present invention time-consuming is short, high-efficient, and reaction condition is mild.The poly butylene succinate molecular weight obtained by the method chain extension can have significant raising compared with the molecular weight before chain extension.Step is simple and convenient to operate, is practical.
Description
Technical Field
The invention belongs to the field of synthesis of high polymer materials, and particularly relates to an efficient chain extension method of poly (butylene succinate).
Background
The poly (butylene succinate) (PBS) serving as a semi-crystalline thermoplastic plastic and biodegradable aliphatic polyester has good biodegradability, excellent molding processability and good mechanical property. It has processability close to that of Polyethylene (PE) and physical properties close to that of polyethylene terephthalate (PET). Compared with degradation plastics such as Polycaprolactone (PCL), Polyhydroxybutyrate (PHB), Polyhydroxyalkanoate (PHA) and the like, PBS has the characteristics of low price, excellent mechanical property and the like; compared with polylactic acid (PLA) with similar price, PBS has the characteristics of convenient processing, adaptability to the conventional plastic processing technology at present and good heat resistance, and the heat distortion temperature can exceed 100 ℃. At present, PBS has been applied to the fields of life production, medicine, agriculture and the like.
With the development of polymer industry and the wide application of polymer materials, the PBS synthesis process has some problems, the most important of which is low molecular weight of the product and many byproducts. At present, the chemical synthesis method is generally adopted for producing PBS at home and abroad. The temperature of PBS synthesized by the direct esterification method and the ester exchange method in the later reaction stage is often over 200 ℃, side reactions such as decarboxylation, thermal degradation and the like can occur, the improvement of relative molecular mass is influenced, and byproducts are generated. The chain extension method for synthesizing PBS has short polymerization time and low equipment requirement. However, most of the existing chain extenders adopt isocyanates, and the chain extenders can easily generate gel in the reaction process, so that the reaction process is difficult to control, and the toxicity of the residual isocyanate also limits the application of the PBS.
Disclosure of Invention
In order to overcome the defects, the invention provides an efficient and rapid chain extension method of poly (butylene succinate), which has low requirements on equipment and can obtain poly (butylene succinate) molecules with higher molecular weight in a short time.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chain extension method of poly (butylene succinate) comprises the following steps:
taking low molecular weight and double-end double-bond poly (butylene succinate) as a prepolymer, and polymerizing the prepolymer by ultraviolet irradiation in the presence of a chain extender and a photoinitiator to obtain the high molecular weight poly (butylene succinate).
The existing chain extenders (epoxy, isocyanate, acid anhydride and oxazoline) mainly utilize the reaction of polyfunctional compounds with carboxyl, hydroxyl, amino and the like in polymers to couple molecular chains, but the molecules after chain extension often contain non-degradable components (such as benzene rings and the like) or cannot be extruded and molded, and besides, the residual isocyanate chain extender also has toxicity. Therefore, the application tries to broaden the synthesis path of the high molecular weight poly (butylene succinate) by modifying the prepolymer to introduce more types of active groups to enrich the types of molecular chain coupling reaction and obtain more types of chain extenders, but because different active groups have different reactivity with PBS and the difficulty of further coupling reaction is different, the invention finds out after large-scale experiments that: by utilizing the mercapto-alkene reaction and taking a dimercapto compound as a chain extender under the irradiation of ultraviolet light, the molecular weight of the poly (butylene succinate) can be greatly improved in a short time, and the prepared high molecular weight poly (butylene succinate) has higher tensile strength and elongation at break.
The polymerization rate of the prior mercaptan olefin system is not only related to the concentration of mercaptan and olefin, but also related to the activity of mercaptan and olefin. In the case of the polybutylene succinate having double terminal bonds of the present invention, the polymerization efficiency using an alkyl mercaptan ester as a chain extender is superior to that of an alkyl 3-mercapto ester thiol or an alkyl (aryl) thiol, and therefore, the preferred chain extender in the present invention is 1, 2-ethanedithiol, 1, 6-hexanedithiol or 1, 8-octanedithiol.
Preferably, the photoinitiator is benzoin anisole or Irgacure 2959.
Theoretically, the chain extender should be used in a molar amount equal to the initial double bond of the prepolymer for the best chain extension. However, the research finds that: when the mass fraction of the chain extender reaches 1-5% of that of the prepolymer, the effect is optimal.
Preferably, the mass ratio of the prepolymer, the chain extender and the photoinitiator is 100: 1-5: 0.01 to 1.
Preferably, the wavelength of the ultraviolet light is 365nm, and the illumination time is 5-25 min.
Preferably, the preparation method of the polybutylene succinate with double-end double bonds comprises the following steps: polymerizing hydroxyl-terminated polybutylene succinate and undecylenic acid in the presence of a catalyst to obtain the product.
Preferably, the catalyst is tetrabutyl titanate.
Preferably, the mass ratio of the hydroxyl-terminated polybutylene succinate to the undecylenic acid to the tetrabutyl titanate is 100: 20-40: 0.1 to 1.
Preferably, the polymerization reaction temperature is 150-175 ℃, and the time is 2-4 h.
The invention also provides high molecular weight polybutylene succinate prepared by any one of the methods.
The invention has the advantages of
(1) The chain extension method of the poly (butylene succinate) provided by the invention is based on click chemistry, and can greatly improve the molecular weight of the poly (butylene succinate) in a short time by using a dimercapto compound as a chain extender under the irradiation of ultraviolet light by utilizing a mercapto-alkene reaction. The click chemistry has the advantages of fast reaction, good selectivity and high product yield, so the method has the advantages of simplicity, high synthesis efficiency, convenience and the like. On the other hand, one of the chain extenders used is 1, 6-hexanedithiol, which is a permissible food additive and also solves the problem that the isocyanate which is a conventional chain extender has toxicity per se.
(2) The synthesis method is simple, the product has high molecular weight and strong practicability, and is easy to popularize.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
An efficient chain extension method of poly (butylene succinate) comprises the following steps:
adding hydroxyl-terminated polybutylene succinate, undecylenic acid and a catalyst tetrabutyl titanate into a reactor for terminal modification. And (3) dissolving the modified double-bond-terminated polybutylene succinate in chloroform, adding a chain extender and a photoinitiator, and irradiating for a certain time by ultraviolet light to obtain the high-molecular-weight polybutylene succinate.
The synthetic route is as follows:
wherein M is poly butylene succinate with different polymerization degrees, and R is straight-chain alkane with carbon atoms of 2,6 and 8.
Preferably, in the synthesis process of the terminal double-bond poly (butylene succinate): the added undecylenic acid accounts for 20-40% of the total mass of the hydroxyl-terminated poly (butylene succinate), the reaction temperature is 150-175 ℃, and the reaction time is controlled to be 2-4 h.
Preferably, in the synthesis process of the terminal double-bond poly (butylene succinate): the mass of the added tetrabutyl titanate is 0.1-1% of the total mass of the hydroxyl-terminated polyester.
Preferably, the chain extender is 1, 2-ethanedithiol, 1, 6-hexanedithiol or 1, 8-octanedithiol.
Preferably, the addition amount of the chain extender is 1-5% of the mass of the terminal double-bond polybutylene succinate.
Preferably, the photoinitiator is benzoin anisole or Irgacure 2959.
Preferably, the dosage of the photoinitiator is 0.01-1% of the mass of the prepolymer.
Preferably, the wavelength of the ultraviolet light is 365nm, and the intensity of the ultraviolet light is 40mW/cm2The reaction time is 5-25 min.
In the following examples of the present invention, molecular weight of polybutylene succinate was measured by a model 1515 gel permeation chromatograph manufactured by Waters corporation, USA, wherein chloroform was used as a mobile phase, the mass concentration of the solution was 0.5%, and the outflow rate was 1.0 mL/min.
Example 1
Under the protection of nitrogen, adding hydroxyl-terminated polybutylene succinate and undecylenic acid into a reactor, wherein the mass of the undecylenic acid is 40% of that of the hydroxyl-terminated polyester, adding a catalyst tetrabutyl titanate accounting for 1% of that of the hydroxyl-terminated polyester, controlling the temperature to be 175 ℃, and obtaining the double-bond-terminated polybutylene succinate after 4 hours. Dissolving the poly (butylene succinate) with modified tail end in chloroform, adding ethanedithiol and benzoin anisole, wherein the mass of the ethanedithiol and the benzoin anisole are respectively 5% and 1% of the mass of the modified polyester, and passing 365nm ultraviolet light (the ultraviolet light intensity is 40 mW/cm)2) And irradiating for 25min to obtain chain-extended polybutylene succinate.
Example 2
Under the protection of nitrogen, adding hydroxyl-terminated polybutylene succinate and undecylenic acid into a reactor, wherein the mass of the undecylenic acid is 20 percent of that of the hydroxyl-terminated polyester, adding a catalyst tetrabutyl titanate with the mass of 0.1 percent of that of the hydroxyl-terminated polyester, controlling the temperature at 150 ℃, and obtaining double-bond-terminated poly after 2 hoursSuccinic acid butylene glycol ester. Dissolving the poly (butylene succinate) with modified tail end in chloroform, adding ethanedithiol and benzoin anisole, wherein the mass of the ethanedithiol and the benzoin anisole are respectively 1% and 0.01% of the mass of the modified polyester, and passing 365nm ultraviolet light (the ultraviolet light intensity is 40 mW/cm)2) And irradiating for 5min to obtain chain-extended polybutylene succinate.
Example 3
Under the protection of nitrogen, adding hydroxyl-terminated polybutylene succinate and undecylenic acid into a reactor, wherein the mass of the undecylenic acid is 20% of that of the hydroxyl-terminated polyester, adding a catalyst tetrabutyl titanate of which the mass is 0.1% of that of the hydroxyl-terminated polyester, controlling the temperature at 160 ℃, and obtaining the double-bond-terminated polybutylene succinate after 4 hours. Dissolving the terminal modified poly (butylene succinate) in chloroform, adding ethanedithiol and Irgacure2959 with the mass respectively being 3% and 0.1% of the modified polyester, and passing 365nm ultraviolet light (the ultraviolet light intensity is 40 mW/cm)2) And irradiating for 10min to obtain chain-extended polybutylene succinate.
Example 4
Under the protection of nitrogen, adding hydroxyl-terminated polybutylene succinate and undecylenic acid into a reactor, wherein the mass of the undecylenic acid is 25% of that of the hydroxyl-terminated polyester, adding a catalyst tetrabutyl titanate of which the mass is 0.5% of that of the hydroxyl-terminated polyester, controlling the temperature to be 170 ℃, and obtaining the double-bond-terminated polybutylene succinate after 3 hours. Dissolving the poly (butylene succinate) with modified tail end in chloroform, adding 1, 6-hexanedithiol and Irgacure2959 with the mass respectively being 5% and 0.5% of the modified polyester, and passing 365nm ultraviolet light (the ultraviolet light intensity is 40 mW/cm)2) And irradiating for 15min to obtain chain-extended polybutylene succinate.
Example 5
Under the protection of nitrogen, adding hydroxyl-terminated polybutylene succinate and undecylenic acid into a reactor, wherein the mass of the undecylenic acid is 30% of that of the hydroxyl-terminated polyester, adding a catalyst tetrabutyl titanate of which the mass is 0.5% of that of the hydroxyl-terminated polyester, controlling the temperature at 160 ℃, and obtaining the double-bond-terminated polybutylene succinate after 3 hours. Modifying the end of the polybutyleneDissolving butanediol ester in chloroform, adding 1, 6-hexanedithiol and Irgacure2959 with the mass of 3% and 0.3% of the modified polyester respectively, and passing 365nm ultraviolet light (the ultraviolet light intensity is 40 mW/cm)2) And irradiating for 10min to obtain chain-extended polybutylene succinate.
Example 6
Under the protection of nitrogen, adding hydroxyl-terminated polybutylene succinate and undecylenic acid into a reactor, wherein the mass of the undecylenic acid is 30% of that of the hydroxyl-terminated polyester, adding a catalyst tetrabutyl titanate of which the mass is 0.5% of that of the hydroxyl-terminated polyester, controlling the temperature to be 165 ℃, and obtaining the double-bond-terminated polybutylene succinate after 3 hours. Dissolving the end-modified polybutylene succinate in chloroform, adding 1, 8-octanedithiol and benzoin anisole, wherein the mass of the end-modified polybutylene succinate is 4% and 0.5% of that of the modified polyester respectively, and passing 365nm ultraviolet light (the ultraviolet light intensity is 40 mW/cm)2) And irradiating for 15min to obtain chain-extended polybutylene succinate.
TABLE 1 molecular weight and Properties of poly (butylene succinate) before and after chain extension
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (2)
1. A chain extension method of poly (butylene succinate), which is characterized by comprising the following steps:
taking low molecular weight and double-end double-bond poly (butylene succinate) as a prepolymer, and polymerizing the prepolymer by ultraviolet irradiation in the presence of a chain extender and a photoinitiator to obtain high molecular weight poly (butylene succinate); wherein,
the chain extender is 1, 2-ethanedithiol, 1, 6-hexanedithiol or 1, 8-octanedithiol;
the photoinitiator is benzoin anisole or Irgacure 2959;
the mass ratio of the prepolymer to the chain extender to the photoinitiator is 100: 1-5: 0.01 to 1;
the wavelength of the ultraviolet light is 365nm, and the illumination time is 5-25 min;
the preparation method of the poly (butylene succinate) with double-end double bonds comprises the following steps: polymerizing hydroxyl-terminated polybutylene succinate and undecylenic acid in the presence of a catalyst to obtain the compound;
the catalyst is tetrabutyl titanate;
the mass ratio of the hydroxyl-terminated poly (butylene succinate), the undecylenic acid and the tetrabutyl titanate is 100: 20-40: 0.1 to 1;
the polymerization reaction temperature in the preparation method of the poly (butylene succinate) with double-end double bonds is 150-175 ℃, and the time is 2-4 h.
2. High molecular weight polybutylene succinate made by the process of claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391644A (en) * | 1992-05-08 | 1995-02-21 | Showa Highpolymer Co., Ltd. | Polyester injection-molded articles |
| CN1487962A (en) * | 2001-01-26 | 2004-04-07 | 3M | Silylated polyurethane-urea compositions for use in cosmetic applications |
| CN101077905A (en) * | 2007-06-26 | 2007-11-28 | 四川大学 | High molecular weight poly(butylene succinate) and preparation method thereof |
| CN103012757A (en) * | 2012-11-27 | 2013-04-03 | 中国包装科研测试中心 | Preparation method of poly(butylene succinate) |
| CN105367790A (en) * | 2015-12-07 | 2016-03-02 | 江西科技师范大学 | Preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391644A (en) * | 1992-05-08 | 1995-02-21 | Showa Highpolymer Co., Ltd. | Polyester injection-molded articles |
| CN1487962A (en) * | 2001-01-26 | 2004-04-07 | 3M | Silylated polyurethane-urea compositions for use in cosmetic applications |
| CN101077905A (en) * | 2007-06-26 | 2007-11-28 | 四川大学 | High molecular weight poly(butylene succinate) and preparation method thereof |
| CN103012757A (en) * | 2012-11-27 | 2013-04-03 | 中国包装科研测试中心 | Preparation method of poly(butylene succinate) |
| CN105367790A (en) * | 2015-12-07 | 2016-03-02 | 江西科技师范大学 | Preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof |
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