CN115572374A - Poly (terephthalate) -co-sebacate resin and preparation method and application thereof - Google Patents
Poly (terephthalate) -co-sebacate resin and preparation method and application thereof Download PDFInfo
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- CN115572374A CN115572374A CN202211230394.0A CN202211230394A CN115572374A CN 115572374 A CN115572374 A CN 115572374A CN 202211230394 A CN202211230394 A CN 202211230394A CN 115572374 A CN115572374 A CN 115572374A
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- sebacate
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- terephthalate
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- 229940116351 sebacate Drugs 0.000 title claims abstract description 131
- 239000011347 resin Substances 0.000 title claims abstract description 113
- 229920005989 resin Polymers 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 title description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229920000728 polyester Polymers 0.000 claims abstract description 69
- -1 poly (terephthalic acid ester Chemical class 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 36
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000003381 stabilizer Substances 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 25
- 238000005886 esterification reaction Methods 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- AMCTYGGTIWUNMF-UHFFFAOYSA-N 1,6-dioxacyclohexadecane-7,16-dione Chemical group O=C1CCCCCCCCC(=O)OCCCCO1 AMCTYGGTIWUNMF-UHFFFAOYSA-N 0.000 claims description 14
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 13
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010096 film blowing Methods 0.000 abstract description 36
- 239000000463 material Substances 0.000 abstract description 30
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000006260 foam Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a poly (terephthalic acid ester) -co-sebacate resin and a preparation method and application thereof, belonging to the technical field of high polymer materials. A polyester terephthalate-co-sebacate resin having an intrinsic viscosity of 0.8 to 1.1dl/g; the polyester terephthalate-co-sebacate resin is prepared in 800s ‑1 The shear viscosity at a shear rate of 200pa · s or less. The polyester terephthalate-co-sebacate resin obviously improves the film blowing characteristic of the resin by controlling the intrinsic viscosity and the shear viscosity of the resin, and can successfully foam to form a film when the film is blown at a higher speed of 200Kg/h, and the film is continuously blownThe film blowing time is longer than 60 minutes, so that the continuity of film blowing production is ensured; and the longitudinal tensile strength and the transverse tensile strength of the film material can simultaneously reach more than 20MPa, so that the material has excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and in particular relates to a poly (terephthalate) -co-sebacate resin as well as a preparation method and application thereof.
Background
Degraded polyester materials have been widely used, such as films, foams, injection molded articles, and the like. Such materials have good physical properties and can degrade to water and carbon dioxide in compost or natural state, with no potential harm to the environment.
The polyester terephthalate-co-sebacate resin (PBSeT) is one of the most active degradation materials in the research of biodegradable plastics at present. The poly terephthalic ester-co-sebacate resin is a copolymer of butylene sebacate and butylene terephthalate, the resin contains flexible aliphatic chains and rigid aromatic chains, so that the resin has high toughness and high temperature resistance, and due to the existence of ester bonds, the resin has biodegradability at the same time, and is one of the best degradation materials for the market application of the current biodegradable plastics.
The prior poly (terephthalate) -co-sebacate resin is produced by a film blowing process, the film blowing stability is poor when the film is blown at a high speed, so that the continuity of the film blowing production is poor, and the longitudinal tensile strength and the transverse tensile strength of the obtained film are less than 20MPa, so that the requirements of packaging products such as shopping bags, preservative films, garbage bags, express bags and the like cannot be met.
The prior art discloses PBST resin, when the film blowing speed is 175Kg/h, the film forming property of the film material is good, and the continuity of the film blowing production is ensured. However, the above-disclosed PBST resin is directed to improving the continuity of the blown film production at a blowing speed of 175Kg/h, but the tensile strength of the material is deteriorated as the blowing speed is increased, and therefore, it does not solve the technical problems that the continuous blowing time is long and the machine direction tensile strength and the transverse direction tensile strength of the material are simultaneously more than 20MPa when the blowing is performed at a speed of 200 Kg/h.
Disclosure of Invention
The invention aims to solve the technical problems that the continuous film blowing time is short, the film blowing production continuity is poor and the longitudinal/transverse tensile strength of a film material cannot reach 20MPa simultaneously when the conventional poly (terephthalate) -co-sebacate resin is blown at the speed of 200Kg/h, and provides the poly (terephthalate) -co-sebacate resin, the film blowing characteristics of the resin are obviously improved by controlling the intrinsic viscosity and the shear viscosity of the resin, the film can be successfully foamed to form when the film is blown at the higher speed of 200Kg/h, the continuous film blowing time is longer than 60 minutes, and the continuity of the film blowing production is ensured; and the longitudinal tensile strength and the transverse tensile strength of the film material can simultaneously reach more than 20MPa, so that the material has excellent mechanical properties.
Another object of the present invention is to provide a method for preparing a polyester terephthalate-co-sebacate resin.
It is still another object of the present invention to provide a polyester terephthalate-co-sebacate resin for use in the preparation of films.
The above purpose of the invention is realized by the following technical scheme:
a polyester terephthalate-co-sebacate resin, the intrinsic viscosity of which is 0.8 to 1.1dl/g; the polyester terephthalate-co-sebacate resin is prepared in 800s -1 The shear viscosity at a shear rate of 200pa · s or less.
The intrinsic viscosity test method comprises the following steps: and (2) determining the intrinsic viscosity by using an Ubbelohde viscometer, wherein the testing temperature is 25 +/-0.01 ℃, the testing solvent is a phenol-o-dichlorobenzene mixed solution, the mass ratio of phenol to o-dichlorobenzene is 3.
The shear viscosity test method comprises the following steps: measured with a capillary rheometer, test conditions: the temperature is 210 ℃; the diameter of the capillary tube is 1mm; the length of the capillary is 40mm; the measuring range of the pressure sensor is 200MPa; test shear rate of 5000s -1 。
Wherein, it is required to be noted that:
the polyester terephthalate-co-sebacate resin obviously improves the film blowing property of the resin by controlling the intrinsic viscosity and the shear viscosity of the resin, can successfully foam to form a film when blowing the film at a higher speed of 200Kg/h, has continuous film blowing time of more than 60 minutes, and ensures the continuity of film blowing production; and the longitudinal tensile strength and the transverse tensile strength of the film material can simultaneously reach more than 20MPa, so that the material has excellent mechanical properties.
The intrinsic viscosity of the terephthalate-co-sebacate resin is too low, which leads to a significant reduction in the continuous film blowing time and also to a significant reduction in the longitudinal/transverse tensile strength of the material, which is not satisfactory for normal use of the article.
The intrinsic viscosity of the polyester terephthalate-co-sebacate resin is too high, the molecular weight of the polymer is also higher, the molecular gel point is increased, and when the film is blown at high speed, the continuous film blowing time is easy to be shorter; when the intrinsic viscosity reaches a certain degree, the gel state is formed, and even the foaming film cannot be formed.
The polyester terephthalate-co-sebacate resin has overlarge shear viscosity, the more serious molecular chain entanglement, the easier the material degradation is caused in the film blowing process or the shearing process of the resin, the film performance is seriously reduced after the film is formed, and the longitudinal/transverse tensile strength is obviously reduced.
Preferably, the shear viscosity of the polyterephthalate-co-sebacate resin is comprised between 20 and 150pas.
The shearing viscosity of the polyester terephthalate-co-sebacate resin is 20-150Pa s, which is beneficial to further improving the tensile strength of the resin and the film blowing time.
Preferably, the intrinsic viscosity of the polyester terephthalate-co-sebacate resin is 0.9 to 1.05dl/g.
The intrinsic viscosity of the polyester terephthalate-co-sebacate resin is in the range of 0.9 to 1.05dl/g, which is beneficial to prolonging the film blowing time and further improving the film blowing stability of the resin.
Preferably, in the polyester terephthalate-co-sebacate resin, the mass content of the butylene terephthalate unit is 45 to 60%, and the mass content of the butylene sebacate unit is 40 to 55%.
The present invention also provides a method for preparing a poly (terephthalate) -co-sebacate resin, comprising the steps of:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 hours, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3000-5000 Pa within 15min, and reacting at 220-225 ℃ for 1-1.5 hours; then reducing the vacuum degree to 700-900 Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 220-240 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
The method comprises the steps of firstly preparing the terephthalate and the sebacate respectively, finely controlling the reaction conditions of the terephthalate and the sebacate, then mixing the terephthalate and the sebacate to carry out polymerization reaction, and regulating and controlling the vacuum degree and the reaction temperature of the polymerization reaction in a stepped manner, wherein the prepared terephthalate-co-sebacate resin has the intrinsic viscosity of 0.8-1.1 dl/g and the shear viscosity of less than or equal to 200Pa s, the continuous film blowing time is more than 60 minutes, and the continuity of film blowing production is ensured; and the longitudinal tensile strength and the transverse tensile strength of the film material can simultaneously reach more than 20MPa, so that the material has excellent mechanical properties.
In S2, the vacuum degree influences the shear viscosity of the material, the vacuum degree is large, the reduction of the shear viscosity of the material is facilitated, but the vacuum degree is too large, so that the aging speed of the material is accelerated, and the shelf life is influenced.
S2, the intrinsic viscosity of the material is influenced by the reaction temperature, the intrinsic viscosity is too low due to too low reaction temperature, and the strength of the resin is reduced; the reaction temperature is too high, the intrinsic viscosity is higher, and the film blowing stability and the material storage time are reduced.
In order to further reduce the shear viscosity of the material and the aging speed of the material, the vacuum degree is preferably reduced by 3500 to 4500Pa within 15min, and the reaction is carried out for 1 to 1.5 hours at 220 to 225 ℃; then reducing the vacuum degree to 750-850 Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 220-240 ℃; a polyester terephthalate-co-sebacate resin was obtained.
In order to further realize the balance between the intrinsic viscosity of the material and the stable storage of the material, in S2, preferably, the vacuum degree is reduced to 3000-5000 Pa within 15min, and the reaction is carried out for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 700-900 Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 225-235 ℃; a polyester terephthalate-co-sebacate resin was obtained.
Preferably, in S1, the catalyst is one of tetrabutyl orthotitanate or tetraisopropyl orthotitanate.
Preferably, in S1, the stabilizer is one or more of phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate and sodium phosphite.
The prepared poly (terephthalic acid ester) -co-sebacate resin has good longitudinal tensile strength and transverse tensile strength, can be widely applied to preparation of plastic products, and particularly protects the application of the poly (terephthalic acid ester) -co-sebacate resin in preparation of plastic films.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a poly (terephthalic acid ester) -co-sebacate resin, which obviously improves the film blowing property of the resin by controlling the intrinsic viscosity and the shear viscosity of the resin, can successfully bubble to form a film when blowing the film at a higher speed of 200Kg/h, has the continuous film blowing time of more than 60 minutes and ensures the continuity of film blowing production; and the longitudinal tensile strength and the transverse tensile strength of the film material can reach more than 20MPa at the same time, so that the material has excellent mechanical properties.
The preparation method of the poly (terephthalate) -co-sebacate resin provided by the invention has the advantages that the reaction conditions of the terephthalate and the sebacate are finely controlled, and the vacuum degree and the reaction temperature of the polymerization reaction are regulated and controlled in a stepped manner, so that the prepared poly (terephthalate) -co-sebacate resin has the intrinsic viscosity of 0.8-1.1 dl/g and the intrinsic viscosity of 800s -1 A shear viscosity at a shear rate of 200pa · s or less.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A polyester terephthalate-co-sebacate resin, the intrinsic viscosity of which is 1.01dl/g; at 800s -1 Shear viscosity at shear rate of 110pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following specific steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 h, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3900Pa within 15min, and reacting at 220-225 ℃ for 1-1.5 hours; then reducing the vacuum degree to 790Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 230 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizer is triphenyl phosphate.
Example 2
A polyester terephthalate-co-sebacate resin, the intrinsic viscosity of which is 1.04dl/g; at 800s -1 The shear viscosity at shear rate of (a) is 200pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following specific steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 h, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3500Pa within 15min, and reacting for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 700Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 230 ℃; a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizer is triphenyl phosphate.
Example 3
A poly (terephthalate) -co-sebacate resin, the intrinsic viscosity of which is 0.82dl/g; at 800s -1 A shear viscosity at a shear rate of 111pa s;
in the polyester terephthalate-co-sebacate resin, the mass content of the butylene terephthalate unit is 50%, and the mass content of the butylene sebacate unit is 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following specific steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 hours, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3900Pa within 15min, and reacting at 220-225 ℃ for 1-1.5 hours; then reducing the vacuum degree to 790Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 220 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizing agent is triphenyl phosphate.
Example 4
A polyester terephthalate-co-sebacate resin, the intrinsic viscosity of which is 1.09dl/g; at 800s -1 The shear viscosity at shear rate of (a) is 109pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following specific steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 h, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3900Pa within 15min, and reacting at 220-225 ℃ for 1-1.5 hours; then reducing the vacuum degree to 790Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 240 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizer is triphenyl phosphate.
Example 5
A polyester terephthalate-co-sebacate resin, the intrinsic viscosity of which is 0.98dl/g; at 800s -1 The shear viscosity at shear rate of (a) is 20pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of the butylene terephthalate unit is 50%, and the mass content of the butylene sebacate unit is 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 hours, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified product and the sebacate esterified product obtained in the S1, firstly reducing the vacuum degree to 4200Pa within 15min, and reacting for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 810Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 230 ℃; a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizing agent is triphenyl phosphate.
Example 6
A poly (terephthalate) -co-sebacate resin, the intrinsic viscosity of which is 1.01dl/g; at 800s -1 Shear viscosity at shear rate of 110pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following specific steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing with nitrogen, and then heating for esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
heating sebacic acid to a molten state, mixing the sebacic acid with a branching agent and a stabilizing agent, adding the mixture into terephthalate, replacing the terephthalate with nitrogen, and heating to react, wherein the reaction temperature is 195-215 ℃, the reaction time is 3-4 h, and the vacuum degree is 60-65 KPa;
s2, firstly reducing the vacuum degree of the substance obtained in the S1 to 3900Pa within 15min, and reacting for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 790Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 230 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, the stabilizer is triphenyl phosphate, and the branching agent is glycerol.
Comparative example 1
A poly (terephthalate) -co-sebacate resin, the intrinsic viscosity of which is 1.03dl/g; at 800s -1 A shear viscosity at a shear rate of 280pa x s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing with nitrogen, and then heating for esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 h, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 2300Pa within 15min, and reacting for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 550Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 230 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizer is triphenyl phosphate.
Comparative example 2
A poly (terephthalate) -co-sebacate resin, the intrinsic viscosity of which is 0.5dl/g; at 800s -1 The shear viscosity at shear rate of (a) is 107pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 h, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3900Pa within 15min, and reacting at 220-225 ℃ for 1-1.5 hours; then reducing the vacuum degree to 790Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 205 ℃; a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizer is triphenyl phosphate.
Comparative example 3
A polyester terephthalate-co-sebacate resin, the intrinsic viscosity of which is 1.3dl/g; at 800s -1 Shear viscosity at shear rate of 110pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following specific steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 hours, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3900Pa within 15min, and reacting at 220-225 ℃ for 1-1.5 hours; then reducing the vacuum degree to 790Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 245 ℃; a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizer is triphenyl phosphate.
Comparative example 4
A poly (terephthalate) -co-sebacate resin, the intrinsic viscosity of which is 0.71dl/g; at 800s -1 The shear viscosity at shear rate of (a) is 180pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following steps:
s1, putting measured terephthalic acid, sebacic acid and 1, 4-butanediol into a reaction kettle, adding an esterification catalyst and a stabilizer, replacing with nitrogen, heating to 235-245 ℃, and reacting for 4.5-5.5 hours.
S2, firstly reducing the vacuum degree of the obtained substance to 3900Pa within 15min, and reacting for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 790Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 230 ℃; a polyester terephthalate-co-sebacate resin was obtained.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizer is triphenyl phosphate.
Comparative example 5
A polyester terephthalate-co-sebacate resin, the intrinsic viscosity of which is 1.36dl/g; at 800s -1 The shear viscosity at shear rate of (a) is 310pa · s;
in the polyester terephthalate-co-sebacate resin, the mass content of butylene terephthalate units was 50%, and the mass content of butylene sebacate units was 50%.
The preparation method of the polyester terephthalate-co-sebacate resin comprises the following specific steps:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 h, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid ester and the sebacic acid ester obtained in the S1, reducing the vacuum degree to be below 50Pa within 30min, and reacting for 5.5 hours at 255-260 ℃ to obtain the terephthalic acid ester-co-sebacic acid ester resin.
Wherein the catalyst is tetrabutyl orthotitanate, and the stabilizing agent is triphenyl phosphate.
Result detection
The polyester terephthalate-co-sebacate resin is used for preparing a film by a film blowing method, wherein the screw temperature of a film blowing machine is 135 ℃, the film blowing speed is 200Kg/h, and the film thickness is 50 mu m.
Film blowing time: the longer the continuous film blowing time is, the better the film blowing production continuity is;
films made from the above-described polyester terephthalate-co-sebacate resins were tested by the following performance test methods:
tensile strength of the film: according to ISO527-2012 standard method.
The specific test results are shown in the following table:
from the data, the film prepared by the polyester terephthalate-co-sebacate resin can be successfully foamed into a film at a higher speed of 200Kg/h, the continuous film blowing time is more than 60 minutes, and the continuity of film blowing production is ensured; and the longitudinal tensile strength and the transverse tensile strength of the film material can reach more than 20MPa at the same time, so that the material has excellent mechanical properties.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A polyester terephthalate-co-sebacate resin, characterized in that the intrinsic viscosity of the polyester terephthalate-co-sebacate resin is 0.8 to 1.1dl/g; the polyester terephthalate-co-sebacate resin is prepared in 800s -1 The shear viscosity at a shear rate of 200pa · s or less.
2. As claimed in claim 1The polyester terephthalate-co-sebacate resin is characterized in that the polyester terephthalate-co-sebacate resin is used in 800s -1 The shear viscosity at the shear rate of (a) is 20 to 150pas.
3. The terephthalate-co-sebacate resin of claim 1, wherein the intrinsic viscosity of the terephthalate-co-sebacate resin is between 0.9 and 1.05dl/g.
4. The terephthalate-co-sebacate resin according to claim 1, wherein the mass content of butylene terephthalate units is 45 to 60% and the mass content of butylene sebacate units is 40 to 55% in the terephthalate-co-sebacate resin.
5. The method for preparing the polyester terephthalate-co-sebacate resin according to claims 1 to 4, comprising the steps of:
s1, preparing a terephthalic acid esterified substance: mixing terephthalic acid, 1, 4-butanediol and a catalyst, replacing the mixture with nitrogen, heating the mixture to perform esterification reaction to obtain terephthalic acid esterified substance, wherein the reaction temperature is 215-220 ℃, the reaction time is 3-4 h, and the vacuum degree is 50-55 KPa;
preparation of sebacate: mixing sebacic acid, 1, 4-butanediol and a stabilizer, replacing with nitrogen, heating for esterification reaction to obtain a sebacate compound, wherein the reaction temperature is 195-215 ℃, the reaction time is 2-3 hours, and the vacuum degree is 80-85 KPa;
s2, mixing the terephthalic acid esterified substance and the sebacate esterified substance obtained in the S1, reducing the vacuum degree to 3000-5000 Pa within 15min, and reacting at 220-225 ℃ for 1-1.5 hours; then reducing the vacuum degree to 700-900 Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 220-240 ℃; a polyester terephthalate-co-sebacate resin was obtained.
6. The preparation method according to claim 5, wherein in S2, the vacuum degree is reduced to 3500-4500 Pa within 15min, and the reaction is carried out for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 750-850 Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 220-240 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
7. The preparation method according to claim 5, wherein in S2, the vacuum degree is reduced to 3000-5000 Pa within 15min, and the reaction is carried out for 1-1.5 hours at 220-225 ℃; then reducing the vacuum degree to 700-900 Pa within 30min, and reacting for 1-1.5 hours at 230-235 ℃; reducing the vacuum degree to 50-100 Pa within 10min, and reacting for 3-3.5 hours at 225-235 ℃; thus, a polyester terephthalate-co-sebacate resin was obtained.
8. The method according to claim 6, wherein in S1, the catalyst is one of tetrabutyl orthotitanate or tetraisopropyl orthotitanate.
9. The method according to claim 6, wherein the stabilizer in S1 is one or more selected from phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate and sodium phosphite.
10. Use of the terephthalate-co-sebacate resin according to any one of claims 1 to 4 for the preparation of films.
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