CN103130992B - Preparation method of polyadipic acid-butylene terephthalate with high molecular weight - Google Patents
Preparation method of polyadipic acid-butylene terephthalate with high molecular weight Download PDFInfo
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Abstract
The invention belongs to the technology in the preparation field of completely biodegradable fat-aromatic copolyester and in particular relates to a preparation method of polyadipic acid-butylene terephthalate with high molecular weight. The preparation method comprises the following steps of: adding butanediol, adipic acid and terephthalic acid into a reactor; adding a composite catalyst to the reactor for carrying out esterification reaction; and carrying out polycondensation to obtain a product, wherein the composite catalyst is a mixture of metal oxide and titanium organic esters, and the metal oxide is at least one of oxides of Li, Na, K, Mg, Al, Ca, Mn and Co. The composite catalyst is adopted, so that the catalytic efficiency is high, the polymerization reaction velocity is greatly increased and the cost of the product is technically reduced. A stabilizer is added during the polycondensation stage, so that the high-temperature degradation side reaction is reduced, the molecular weight of the polymer is improved, the product color phase is improved, the terminal carboxyl content of the polymer is effectively reduced, the post-processing heat resistant performance of the product is improved, and the using value is greater.
Description
Technical field
The invention belongs to the aliphatic-aromatic copolyester preparation field technology of complete biodegradable, be specifically related to a kind of high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's preparation method.
Background technology
Along with the development of plastics industry, synthesized polymer material is being brought into play extremely important effect in the every field of industrial and agricultural production and daily life, but because of its discarded rear non-degradable, to social life, has brought serious pollution.Seek the plastics that a kind of environmental friendliness can meet again various demands simultaneously and cause numerous scientific workers' attention, in recent years, degradable polyester, due to its degradation characteristic and economy, has become the focus of domestic and international research.
Poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is a kind of polyester material of complete biodegradable wherein, easily by the multiple-microorganism of occurring in nature or animal and plant body endoenzyme decompose, metabolism, finally generate carbonic acid gas and water.Poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester has the characteristic of poly adipate succinic acid ester and polybutylene terephthalate concurrently, existing good ductility and elongation at break, also there are good thermotolerance and impact property, greatly improved the performance of original binary polyester material, and cost is not high, there is larger practical value.
Poly-hexanodioic acid-the mutual-phenenyl two acid bromide two alcohol ester of synthesis of ternary copolyesters still exists a series of problem at present, as adopt original binary polyester catalyst, catalytic efficiency is low, polyreaction is slow, polymericular weight is low, and meanwhile, the polycondensation later stage is because temperature is compared with high and the side reactions such as decarboxylation, cyclisation, thermal destruction easily occur, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester color the jaundice that causes synthesizing, molecular weight reduces and molecular weight distribution is wide, and product performance can not meet the demands.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, has overcome the shortcoming that traditional catalyst catalytic efficiency is low, cost is high; The shortcomings such as melt high temperature is unstable, hue difference have been improved.
High-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's of the present invention preparation method, comprises the steps:
Butyleneglycol, hexanodioic acid and terephthalic acid are placed in to reactor, add composite catalyst, carry out esterification, and then carry out polycondensation, obtain product;
Wherein: composite catalyst is the mixture of metal oxide and titanium organosilane ester, wherein metal oxide is at least one in the oxide compound of Li, Na, K, Mg, Al, Ca, Mn or Co, and titanium organosilane ester is at least one in butyl (tetra) titanate, titanium isopropylate, tetraethyl titanate, two (acetylacetone based) metatitanic acid diisopropyl ester, two (methyl aceto acetate) metatitanic acid diisopropyl ester or two trolamine di-isopropyl titanic acid ester.Metal oxide-type catalyst levels is 0.01%～0.05% of reactant gross weight, and titanium organosilane ester catalyst levels is 0.1%～0.8% of reactant gross weight.Adopt this composite catalyst, shortened polymerization time, catalytic efficiency is high, and polymerization rate increases greatly, from technique, has reduced the cost of product.
Alcohol and sour mol ratio are 1～2:1, and the mol ratio of hexanodioic acid and terephthalic acid is 55～70:30～45.
The temperature of esterification is 180～240 ℃, and reaction pressure is normal pressure, and the reaction times is 1.5～2.5 hours.
The temperature of polycondensation is 220～260 ℃, and reaction pressure is for being decompressed to 10～100Pa, and the reaction times is 2～4 hours.
When carrying out polycondensation, add stablizer.Stablizer is dicyclohexylcarbodiimide, N, a kind of in N'-DIC or their polymkeric substance.Stablizer is reactant gross weight 0.03%～0.1%.Stablizer participates in polycondensation, reduces high temperature degradation side reaction, has improved the molecular weight of polymkeric substance, effectively reduce the content of carboxyl end group of polymkeric substance, not changing under the prerequisite of its biological degradability, greatly improved product mechanical property, thermotolerance and form and aspect, thereby widened its Application Areas.
Poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester molecular weight prepared by the present invention is 8.6 * 10
4～15.2 * 10
4, molecular weight distribution between 1.5～2.0, tensile strength is 17～21MPa, elongation at break is 600～800%.Molecular weight product is high, narrow molecular weight distribution, form and aspect are good, mechanical property is excellent, improved the resistance toheat of product post-production.
In sum, the present invention has the following advantages:
(1) adopt composite catalyst, catalytic efficiency is high, and polymerization rate increases greatly, from technique, has reduced the cost of product;
(2) polycondensation phase adds stablizer, has reduced high temperature degradation side reaction, has improved the molecular weight of polymkeric substance, improves product form and aspect, effectively reduces the content of carboxyl end group of polymkeric substance, has improved the resistance toheat of product post-production, has larger use value.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
By 136g butyleneglycol, 80g hexanodioic acid and 75g terephthalic acid as in reactor, stir, adding the two trolamine di-isopropyl titanic acid ester of composite catalyst 0.058g MgO and 0.29g, is to carry out normal pressure esterification, isothermal reaction 2.3 hours under the condition of 180 ℃ in temperature.Then, be warming up to 220 ℃, add 0.087g stablizer polycarbodiimide, be decompressed to 30Pa and carry out polycondensation, react 3 hours, the poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester molecular weight obtaining is 9.4 * 10
4, molecular weight distribution is 1.62, and tensile strength is 18.21MPa, and elongation at break is 743%, L value 82, acid number 18.6mol/t.
Embodiment 2
180g butyleneglycol, 102g hexanodioic acid and 50g terephthalic acid, as in reactor, are stirred, add composite catalyst 0.166g Al
2o
3with 2.65g bis-(methyl aceto acetate) metatitanic acid diisopropyl ester, in temperature, be to carry out normal pressure esterification, isothermal reaction 1.5 hours under the condition of 230 ℃.Then, be warming up to 250 ℃, add 0.332g stablizer dicyclohexylcarbodiimide, be decompressed to 50Pa and carry out polycondensation, react 3.5 hours, the poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester molecular weight obtaining is 15.2 * 10
4, molecular weight distribution is 1.87, and tensile strength is 17.42MPa, and elongation at break is 795%, L value 81, acid number 20.2mol/t.
Embodiment 3
92g butyleneglycol, 88g hexanodioic acid and 66g terephthalic acid, as in reactor, are stirred, add composite catalyst 0.025g Li
2o and 1.23g tetraethyl titanate are to carry out normal pressure esterification, isothermal reaction 2 hours under the condition of 215 ℃ in temperature.Then, be warming up to 230 ℃, add 0.123g stablizer polycarbodiimide, be decompressed to 80Pa and carry out polycondensation, react 2.5 hours, the poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester molecular weight obtaining is 11.9 * 10
4, molecular weight distribution is 1.57, and tensile strength is 20.91MPa, and elongation at break is 602%, L value 85, acid number 16.7mol/t.
Embodiment 4
By 134g butyleneglycol, 74g hexanodioic acid and 83g terephthalic acid as in reactor, stir, adding composite catalyst 0.087g CaO and 0.58g bis-(acetylacetone based) metatitanic acid diisopropyl ester, is to carry out normal pressure esterification, isothermal reaction 2.5 hours under the condition of 200 ℃ in temperature.Then, be warming up to 240 ℃, add 0.116g stablizer N, N'-DIC, is decompressed to 100Pa and carries out polycondensation, reacts 4 hours, and the poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester molecular weight obtaining is 8.6 * 10
4, molecular weight distribution is 1.73, and tensile strength is 19.11MPa, and elongation at break is 695%, L value 79, acid number 22.5mol/t.
Embodiment 5
153g butyleneglycol, 95g hexanodioic acid and 58g terephthalic acid, as in reactor, being stirred, add composite catalyst 0.116g CoO and 2.14g titanium isopropylate, is to carry out normal pressure esterification, isothermal reaction 1.8 hours under the condition of 240 ℃ in temperature.Then, be warming up to 260 ℃, add 0.248g stablizer polycarbodiimide, be decompressed to 10Pa and carry out polycondensation, react 2 hours, the poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester molecular weight obtaining is 14.7 * 10
4, molecular weight distribution is 1.83, and tensile strength is 17.12MPa, and elongation at break is 723%, L value 80, acid number 18.1mol/t.
Claims (6)
1. high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's a preparation method, is characterized in that: comprise the steps:
Butyleneglycol, hexanodioic acid and terephthalic acid are placed in to reactor, add composite catalyst, carry out esterification, and then carry out polycondensation, obtain product;
Wherein: composite catalyst is the mixture of metal oxide and titanium organosilane ester, wherein metal oxide is at least one in the oxide compound of Li, Na, K, Mg, Al, Ca, Mn or Co, and titanium organosilane ester is at least one in butyl (tetra) titanate, titanium isopropylate, tetraethyl titanate, two (acetylacetone based) metatitanic acid diisopropyl ester, two (methyl aceto acetate) metatitanic acid diisopropyl ester or two trolamine di-isopropyl titanic acid ester;
When carrying out polycondensation, add stablizer;
Wherein stablizer is dicyclohexylcarbodiimide, N, a kind of in N'-DIC or their polymkeric substance.
2. high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's according to claim 1 preparation method, it is characterized in that: metal oxide-type catalyst levels is 0.01%～0.05% of reactant gross weight, titanium organosilane ester catalyst levels is 0.1%～0.8% of reactant gross weight.
3. high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's according to claim 1 preparation method, is characterized in that: alcohol and sour mol ratio are 1～2:1, and the mol ratio of hexanodioic acid and terephthalic acid is 55～70:30～45.
4. high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's according to claim 1 preparation method, is characterized in that: the temperature of esterification is 180～240 ℃, and reaction pressure is normal pressure, and the reaction times is 1.5～2.5 hours.
5. high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's according to claim 1 preparation method, is characterized in that: the temperature of polycondensation is 220～260 ℃, and reaction pressure is for being decompressed to 10～100Pa, and the reaction times is 2～4 hours.
6. high-molecular-weight poly hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester's according to claim 1 preparation method, is characterized in that: stablizer is reactant gross weight 0.03%～0.1%.
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| CN105732959A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of ultraviolet ray resistant and hydrolysis resistant polyester material |
| CN105733202A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Ultraviolet ray resistant and hydrolysis resistant polyester material and photovoltaic cell backboard |
| CN108727572A (en) * | 2018-05-21 | 2018-11-02 | 金晖兆隆高新科技股份有限公司 | The synthetic method for the high resiliency spinning adaptive type biodegradation resin that hot property is stablized |
| CN112080000B (en) * | 2020-09-29 | 2021-04-23 | 广州市海珥达环保科技有限公司 | Method for synthesizing poly (p-phthalic acid) -adipic acid-m-epoxy pentadecyl phenol butanediol |
| CN112266471B (en) * | 2020-11-13 | 2022-08-05 | 康辉新材料科技有限公司 | Preparation method of polybutylene adipate-terephthalate |
| CN112574053B (en) * | 2020-12-11 | 2022-03-04 | 江苏极易新材料有限公司 | Synthesis process of antioxidant 1098 |
| CN113667103B (en) * | 2021-08-30 | 2022-11-04 | 万华化学集团股份有限公司 | Preparation method of PBAT resin |
| CN113831518B (en) * | 2021-11-15 | 2022-04-12 | 中核华纬工程设计研究有限公司 | Method for modifying PBAT (poly (butylene adipate-co-terephthalate)) by using small-molecular phenol |
| CN115197403B (en) * | 2022-09-01 | 2023-05-26 | 东北师范大学 | Crystalline degradable polyester based on 1, 3-butanediol and preparation method thereof |
| CN115612074A (en) * | 2022-10-17 | 2023-01-17 | 南通天洋新材料有限公司 | Preparation method of biodegradable polyester |
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