CN102120721B - Method for preparing epoxy resin curing agent by degrading polyethylene terephthalate with glycerine - Google Patents
Method for preparing epoxy resin curing agent by degrading polyethylene terephthalate with glycerine Download PDFInfo
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- CN102120721B CN102120721B CN2011100059105A CN201110005910A CN102120721B CN 102120721 B CN102120721 B CN 102120721B CN 2011100059105 A CN2011100059105 A CN 2011100059105A CN 201110005910 A CN201110005910 A CN 201110005910A CN 102120721 B CN102120721 B CN 102120721B
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Abstract
A method for preparing epoxy resin curing agent by degrading polyethylene terephthalate (PET) with glycerine relates to the technical field of the preparation of the epoxy resin curing agent. The method comprises the following steps: adding glycerine and ZnAc2 used as catalyst in a four-necked flask in turn according to a certain ratio, fixing the four-necked flask on an electric mixer, slowly heating to ensure that catalyst is completely dissolved, introducing nitrogen, then adding polyethylene terephthalate continuously heating to ensure that PET is completely dissolved, starting the mixer to react; cooling the reaction product, transferring the reaction product to a reduced pressure distillation device to obtain an intermediate product after the reduced pressure distillation; and adding the intermediate product and sodium methylate used as catalyst in the four-necked flask, continuously dropping diethanol amine in the reaction system with a constant pressure funnel, and controlling the reaction temperature to react and obtain the epoxy resin curing agent. By adopting the invention, the epoxy resin curing agent which has the functions such as curing, toughening, antiflaming and promoting and is characterized by fast curing, low-temperature curing, low water absorption and the like, can be prepared.
Description
Technical field
The present invention relates to Resins, epoxy and make the field, is a kind of method for preparing epoxy curing agent with glycerol degraded PET.
Background technology
Polyester PET has outstanding physical and chemical performance, is widely used as synthon, packing plastic bottle, film, matrix material, copolymerization type material and biomedicine field always.But because polyester is difficult under field conditions (factors) by biological degradation, a large amount of waste polyesters has brought heavy pressure to environment, and therefore, the degraded of waste polyester is still at present the emphasis of research both at home and abroad.Being widely used of Resins, epoxy can be used as tackiness agent, and coating etc. are used for fields such as building, aviation and navigation, automobile, electronics.If but Resins, epoxy does not have itself utility value of proper curing agents very little, if can develop novel solidifying agent, make it have functions such as curing, toughness reinforcing, fire-retardant, promotion concurrently, and have characteristics such as fast setting, low-temperature curing and water-intake rate are little, will have major contribution in this field of epoxy curing agent so.The present invention has prepared epoxy curing agent after polyester PET is degraded, and has both alleviated the pressure that PET industry brings environment, has realized environmental protection, has prepared the neo-epoxy resin solidifying agent again, kills two birds with one stone, and great Research Significance is arranged.
Summary of the invention
The objective of the invention is to, a kind of method for preparing epoxy curing agent with glycerol degraded polyester PET is provided.
Technical scheme of the present invention: a kind of method of utilizing glycerol degraded PET to prepare epoxy curing agent, the principle by transesterification reaction, dehydration condensation and ring-opening polymerization prepares epoxy curing agent:
(1) reaction unit is installed: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls; Four-hole boiling flask is fixed on the electric mixing device;
(2) DeR: in four-hole boiling flask, add 500～700 parts of glycerol, 0.1～0.3 part of catalyst acetic acid zinc ZnAc
2, slowly be warming up to logical nitrogen after the complete fusion of catalyzer; Add 100～200 parts of polyethylene terephtalates, continue to be warming up to 290 ℃, treat to open electric mixing device after PET dissolves fully, the control rotating speed is at 150～200r/min, reaction 2～3h obtains pale brown look thick product and faint yellow transparence cut; Unit is weight part;
(3) underpressure distillation: the thick product of the pale brown look of step (2) gained is cooled to 135～145 ℃, pours in the vacuum distillation apparatus; Control vacuum distillation temperature be 190 ℃ of distillations, to do not have cut be isolated as the distillation finish, obtain intermediate product;
(4) preparation of epoxy curing agent: (3) gained intermediate product set by step: diethanolamine: the mol ratio of catalyzer sodium methylate is that 1: 1～1.2: 0.01 ratio takes by weighing diethanolamine and sodium methylate, intermediate product and sodium methylate are inserted four-hole boiling flask, the flask four-hole connects thermometer respectively, electric mixing device and constant pressure funnel, another mouthful sealing, whole four-hole boiling flask places water-bath, heat up, when reaching 90 ℃, reacting liquid temperature in reaction system, constantly drips diethanolamine by constant pressure funnel, whole process control temperature of reaction is at 90 ℃, reaction 3～5h obtains the product epoxy curing agent.
Intermediate product described in the step (4): diethanolamine: the mol ratio of catalyzer sodium methylate is 1: 1.2: 0.01.
The described intermediate product relative molecular mass of step (3) is 296g/mol, and molecular formula is as follows:
Product epoxy curing agent intermediate end has epoxide group, and solubility property is good, water-soluble during room temperature, pure, aldehydes solvent, and its oxirane value of surveying according to the described hydrochloric acid of GB/T167-1981-acetone method is 0.3 equivalent/100 grams.
The effect of above-mentioned each raw material: PET is reaction raw materials.Glycerol is as degradation agents, the effect that had both had solvent, catalyzer and polyester PET can be dissolved wherein, be conducive to the carrying out that react, again as the transesterify agent, can with the terephthalic acid ethylene glycol (BHET) that generates after the PET chain rupture in ethylene glycol instead give birth to transesterify, obtain the terephthalic acid glycerol.Zinc acetate ZnAc
2As catalyzer, be conducive to add the carrying out of fast response.Sodium methylate is conducive to the carrying out of catalysis ring-opening reaction as basic catalyst.Hydrogen activity in the diethanolamine on the nitrogen element is very high, can react with epoxy group.
Hot conditions can improve the catalytic activity of catalyzer, and accelerated reaction is again the boiling point of glycerol, and the boiling point that is higher than ethylene glycol, like this, can make and not participate in the glycerol of reaction and fractionate out reaction system by the ethylene glycol that transesterify obtains, improve product purity.
Beneficial effect of the present invention: utilize the present invention to prepare to have concurrently functions such as curing, toughness reinforcing, fire-retardant, promotion, and the novel solidifying agent with characteristics such as fast setting, low-temperature curing and water-intake rate are little, both alleviated the pressure that PET industry brings environment, realized environmental protection, prepared the neo-epoxy resin solidifying agent again, kill two birds with one stone, great meaning is arranged.
Embodiment
The invention will be further elaborated by the following examples, its objective is to be better understanding content of the present invention.Therefore, for example does not influence protection scope of the present invention:
Embodiment 1
(1) reaction unit is installed: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls; Four-hole boiling flask is fixed on the electric mixing device;
(2) DeR: in four-hole boiling flask, add 500 parts of glycerol, 0.1 part of catalyst acetic acid zinc ZnAc
2, slowly be warming up to logical nitrogen after the complete fusion of catalyzer; Add 100 parts of polyethylene terephtalates, continue to be warming up to 290 ℃, treat to open electric mixing device after PET dissolves fully, the control rotating speed is at 150r/min, and reaction 2.5h obtains pale brown look thick product and faint yellow transparence cut; Unit is weight part, down together;
(3) underpressure distillation: the thick product of the pale brown look of step (2) gained is cooled to 145 ℃, pours in the vacuum distillation apparatus; Control vacuum distillation temperature be 190 ℃ of distillations, to do not have cut be isolated as the distillation finish, obtain intermediate product;
(4) preparation of epoxy curing agent: (3) gained intermediate product set by step: diethanolamine: the mol ratio of catalyzer sodium methylate is that 1: 1: 0.01 ratio takes by weighing diethanolamine and sodium methylate, intermediate product and sodium methylate are inserted four-hole boiling flask, the flask four-hole connects thermometer respectively, electric mixing device and constant pressure funnel, another mouthful sealing, whole four-hole boiling flask places water-bath, heat up, when reaching 90 ℃, reacting liquid temperature in reaction system, constantly drips diethanolamine by constant pressure funnel, whole process control temperature of reaction is at 90 ℃, reaction 3h, obtain the product epoxy curing agent, productive rate is 73.3%.With this solidifying agent and E-PON828 (bisphenol A-type glycidyl ester) with amido: epoxy group(ing) is to be mixed with epoxy coating at 1: 1, and coating thickness is 1mm, film formation time 2h, snappiness is good, shock-resistance is 50kgcm.
Embodiment 2
(1) reaction unit is installed: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls; Four-hole boiling flask is fixed on the electric mixing device;
(2) DeR: in four-hole boiling flask, add 600 parts of glycerol, 0.2 part of catalyst acetic acid zinc ZnAc
2, slowly be warming up to logical nitrogen after the complete fusion of catalyzer; Add 150 parts of polyethylene terephtalates, continue to be warming up to 290 ℃, treat to open electric mixing device after PET dissolves fully, the control rotating speed is at 200r/min, and reaction 3h obtains pale brown look thick product and faint yellow transparence cut;
(3) underpressure distillation: the thick product of the pale brown look of step (2) gained is cooled to 140 ℃, pours in the vacuum distillation apparatus; Control vacuum distillation temperature be 190 ℃ of distillations, to do not have cut be isolated as the distillation finish, obtain intermediate product;
(4) preparation of epoxy curing agent: (3) gained intermediate product set by step: diethanolamine: the mol ratio of catalyzer sodium methylate is that 1: 1.1: 0.01 ratio takes by weighing diethanolamine and sodium methylate, intermediate product and sodium methylate are inserted four-hole boiling flask, the flask four-hole connects thermometer respectively, electric mixing device and constant pressure funnel, another mouthful sealing, whole four-hole boiling flask places water-bath, heat up, when reaching 90 ℃, reacting liquid temperature in reaction system, constantly drips diethanolamine by constant pressure funnel, whole process control temperature of reaction is at 90 ℃, reaction 4h, obtain the product epoxy curing agent, productive rate is 82.7%.This solidifying agent and E-PON828 are mixed with epoxy coating, and coating thickness is 1mm, film formation time 2h, and snappiness is good, and shock-resistance is 50kgcm.
Embodiment 3
(1) reaction unit is installed: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls; Four-hole boiling flask is fixed on the electric mixing device;
(2) DeR: in four-hole boiling flask, add 700 parts of glycerol, 0.3 part of catalyst acetic acid zinc ZnAc
2, slowly be warming up to logical nitrogen after the complete fusion of catalyzer; Add 200 parts of polyethylene terephtalates, continue to be warming up to 290 ℃, treat to open electric mixing device after PET dissolves fully, the control rotating speed is at 200r/min, and reaction 3h obtains pale brown look thick product and faint yellow transparence cut;
(3) underpressure distillation: the thick product of the pale brown look of step (2) gained is cooled to 145 ℃, pours in the vacuum distillation apparatus; Control vacuum distillation temperature be 190 ℃ of distillations, to do not have cut be isolated as the distillation finish, obtain intermediate product;
(4) preparation of epoxy curing agent: (3) gained intermediate product set by step: diethanolamine: the mol ratio of catalyzer sodium methylate is that 1: 1.2: 0.01 ratio takes by weighing diethanolamine and sodium methylate, intermediate product and sodium methylate are inserted four-hole boiling flask, the flask four-hole connects thermometer respectively, electric mixing device and constant pressure funnel, another mouthful sealing, whole four-hole boiling flask places water-bath, heat up, when reaching 90 ℃, reacting liquid temperature in reaction system, constantly drips diethanolamine by constant pressure funnel, whole process control temperature of reaction is at 90 ℃, reaction 5h, obtain the product epoxy curing agent, productive rate is 92.5%.This solidifying agent and E-PON828 are mixed with epoxy coating, and coating thickness is 1mm, film formation time 2h, and snappiness is good, and shock-resistance is 50kgcm.
Embodiment 4
(1) reaction unit is installed: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls; Four-hole boiling flask is fixed on the electric mixing device;
(2) DeR: in four-hole boiling flask, add 550 parts of glycerol, 0.2 part of catalyst acetic acid zinc ZnAc
2, slowly be warming up to logical nitrogen after the complete fusion of catalyzer; Add 150 parts of polyethylene terephtalates, continue to be warming up to 290 ℃, treat to open electric mixing device after PET dissolves fully, the control rotating speed is at 175r/min, and reaction 2h obtains pale brown look thick product and faint yellow transparence cut;
(3) underpressure distillation: the thick product of the pale brown look of step (2) gained is cooled to 135 ℃, pours in the vacuum distillation apparatus; Control vacuum distillation temperature be 190 ℃ of distillations, to do not have cut be isolated as the distillation finish, obtain intermediate product;
(4) preparation of epoxy curing agent: (3) gained intermediate product set by step: diethanolamine: the mol ratio of catalyzer sodium methylate is that 1: 1: 0.01 ratio takes by weighing diethanolamine and sodium methylate, intermediate product and sodium methylate are inserted four-hole boiling flask, the flask four-hole connects thermometer respectively, electric mixing device and constant pressure funnel, another mouthful sealing, whole four-hole boiling flask places water-bath, heat up, when reaching 90 ℃, reacting liquid temperature in reaction system, constantly drips diethanolamine by constant pressure funnel, whole process control temperature of reaction is at 90 ℃, reaction 3h, obtain the product epoxy curing agent, productive rate is 92.8%.This solidifying agent and E-PON828 are mixed with epoxy coating, and coating thickness is 1mm, film formation time 2h, and snappiness is good, and shock-resistance is 50kgcm.
Embodiment 5
(1) reaction unit is installed: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls; Four-hole boiling flask is fixed on the electric mixing device;
(2) DeR: in four-hole boiling flask, add 650 parts of glycerol, 0.3 part of catalyst acetic acid zinc ZnAc
2, slowly be warming up to logical nitrogen after the complete fusion of catalyzer; Add 175 parts of polyethylene terephtalates, continue to be warming up to 290 ℃, treat to open electric mixing device after PET dissolves fully, the control rotating speed is at 150r/min, and reaction 3h obtains pale brown look thick product and faint yellow transparence cut;
(3) underpressure distillation: the thick product of the pale brown look of step (2) gained is cooled to 140 ℃, pours in the vacuum distillation apparatus; Control vacuum distillation temperature be 190 ℃ of distillations, to do not have cut be isolated as the distillation finish, obtain intermediate product;
(4) preparation of epoxy curing agent: (3) gained intermediate product set by step: diethanolamine: the mol ratio of catalyzer sodium methylate is that 1: 1.1: 0.01 ratio takes by weighing diethanolamine and sodium methylate, intermediate product and sodium methylate are inserted four-hole boiling flask, the flask four-hole connects thermometer respectively, electric mixing device and constant pressure funnel, another mouthful sealing, whole four-hole boiling flask places water-bath, heat up, when reaching 90 ℃, reacting liquid temperature in reaction system, constantly drips diethanolamine by constant pressure funnel, whole process control temperature of reaction is at 90 ℃, reaction 5h, obtain the product epoxy curing agent, productive rate is 68.2%.This solidifying agent and E-PON828 are mixed with epoxy coating, and coating thickness is 1mm, film formation time 2h, and snappiness is good, and shock-resistance is 50kgcm.
Claims (2)
1. a method of utilizing glycerol degraded PET to prepare epoxy curing agent is characterized in that, the principle by transesterification reaction, dehydration condensation and ring-opening polymerization prepares epoxy curing agent:
(1) reaction unit is installed: getting four-hole boiling flask is reaction vessel, wherein settles thermometer, reflux condensate device and logical nitrogen device respectively for three mouthfuls; Four-hole boiling flask is fixed on the electric mixing device;
(2) DeR: add 500 ~ 700 parts of glycerol in four-hole boiling flask, 0.1 ~ 0.3 part of catalyst acetic acid zinc slowly is warming up to logical nitrogen after the complete fusion of catalyzer; Add 100 ~ 200 parts of polyethylene terephtalates, continue to be warming up to 290 ℃, treat to open electric mixing device after PET dissolves fully, the control rotating speed is at 150 ~ 200r/min, and reaction 2 ~ 3h obtains pale brown look thick product and faint yellow transparence cut; Unit is weight part;
(3) underpressure distillation: the thick product of the pale brown look of step (2) gained is cooled to 135 ~ 145 ℃, pours in the vacuum distillation apparatus; Control vacuum distillation temperature be 190 ℃ of distillations, to do not have cut be isolated as the distillation finish, obtain intermediate product;
(4) preparation of epoxy curing agent: (3) gained intermediate product set by step: diethanolamine: the mol ratio of catalyzer sodium methylate is that the ratio of 1:1 ~ 1.2:0.01 takes by weighing diethanolamine and sodium methylate, intermediate product and sodium methylate are inserted four-hole boiling flask, the flask four-hole connects thermometer respectively, electric mixing device and constant pressure funnel, another mouthful sealing, whole four-hole boiling flask places water-bath, heat up, when reaching 90 ℃, reacting liquid temperature in reaction system, constantly drips diethanolamine by constant pressure funnel, whole process control temperature of reaction is at 90 ℃, reaction 3 ~ 5h obtains the product epoxy curing agent.
2. according to the described method of utilizing glycerol degraded PET to prepare epoxy curing agent of claim 1, it is characterized in that described intermediate product: diethanolamine: the mol ratio of catalyzer sodium methylate is 1:1.2:0.01.
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| CN2011100059105A CN102120721B (en) | 2011-01-12 | 2011-01-12 | Method for preparing epoxy resin curing agent by degrading polyethylene terephthalate with glycerine |
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| CN2011100059105A CN102120721B (en) | 2011-01-12 | 2011-01-12 | Method for preparing epoxy resin curing agent by degrading polyethylene terephthalate with glycerine |
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| CN102120721B true CN102120721B (en) | 2013-08-07 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289060A (en) * | 2012-03-02 | 2013-09-11 | 江南大学 | Method for preparing epoxy resin curing agent through utilizing ethylene glycol to depolymerize polyethylene glycol terephthalate (PET) |
| CN103289121A (en) * | 2012-03-02 | 2013-09-11 | 江南大学 | Method for depolymerizing PET (polyethylene terephthalate) with glycerol |
| CN102701985A (en) * | 2012-06-12 | 2012-10-03 | 唐海峰 | Method for preparing epoxy resin curing agent by performing alcoholysis on PET (Polyethylene Terephthalate) polyester |
| CN103897144A (en) * | 2012-12-26 | 2014-07-02 | 江南大学 | Method used for preparing nano composite epoxy curing agent via depolymerization of PET with glycerine |
| CN104479168A (en) * | 2014-11-18 | 2015-04-01 | 广东树业环保科技股份有限公司 | Waste PET (polyethylene terephthalate) decolorization recovery method, product and application |
| CN104725260B (en) * | 2015-01-22 | 2017-08-29 | 漳州亚邦化学有限公司 | The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD125037A3 (en) * | 1972-07-11 | 1977-03-30 | ||
| CN1957027A (en) * | 2004-03-26 | 2007-05-02 | 金度均 | Recycled method for a wasted polymer which is mixed polyester polyamide and reclaimed materials thereof |
-
2011
- 2011-01-12 CN CN2011100059105A patent/CN102120721B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD125037A3 (en) * | 1972-07-11 | 1977-03-30 | ||
| CN1957027A (en) * | 2004-03-26 | 2007-05-02 | 金度均 | Recycled method for a wasted polymer which is mixed polyester polyamide and reclaimed materials thereof |
Non-Patent Citations (4)
| Title |
|---|
| 周文聪等.废弃PET聚酯醇解技术进展.《武汉科技学院学报》.2008,第21卷(第12期),第15-18页. |
| 废弃PET聚酯醇解技术进展;周文聪等;《武汉科技学院学报》;20081231;第21卷(第12期);第15-18页 * |
| 废旧PET聚酯塑料循环利用的应用研究进展;王慧等;《工程研究—跨学科视野中的工程》;20091231;第1卷(第4期);第305-313页 * |
| 王慧等.废旧PET聚酯塑料循环利用的应用研究进展.《工程研究—跨学科视野中的工程》.2009,第1卷(第4期),第305-313页. |
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