CN103554380A - Process for preparing unsaturated polyester resin by mixed alcohol alcoholysis of RPET (recycled polyethylene terephtalate) plastic - Google Patents
Process for preparing unsaturated polyester resin by mixed alcohol alcoholysis of RPET (recycled polyethylene terephtalate) plastic Download PDFInfo
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- CN103554380A CN103554380A CN201310556734.3A CN201310556734A CN103554380A CN 103554380 A CN103554380 A CN 103554380A CN 201310556734 A CN201310556734 A CN 201310556734A CN 103554380 A CN103554380 A CN 103554380A
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Abstract
The invention belongs to the technical field of synthesis of unsaturated polyester resin and particularly discloses a process for preparing unsaturated polyester resin by mixed alcohol alcoholysis of RPET (recycled polyethylene terephtalate) plastic. The main technical scheme is as follows: adding the mixed alcohol, a catalyst and the RPET plastic into a reaction kettle to carry out a degradation reaction, and then, adding phthalic anhydride and maleic anhydride into the reaction kettle to carry out an esterification polymerization reaction, and adding a polymerization inhibitor and a diluent after the reaction is finished to obtain the unsaturated polyester resin. By adopting the process of utilizing the mixed alcohol as an alcoholysis agent to degrade the RPET plastic so as to produce the unsaturated polyester resin, the environmental pollution problem is solved, relatively considerable economic benefit is brought to the enterprise, and technical support is provided for the reclamation of the RPET and the comprehensive utilization of the mixed alcohol as well.
Description
Technical field
The invention belongs to unsaturated polyester resin production technical field, relate to concretely a kind of alcohol mixture alcoholysis waste PET resin that utilizes for the technique of unsaturated polyester resin.
Background technology
Polyethylene terephthalate was succeeded in developing by British scientist in nineteen forty-one, and within 1949, Britain ICI company successfully develops and takes the lead in realizing suitability for industrialized production in nineteen fifty-three.Because social demand constantly increases, PET polyester output rapid growth, since two thousand three, global PET production capacity is expanded rapidly with the speed of average annual 9% left and right, ends 2005 annual capacities and has reached approximately 5,470 ten thousand tons, and output is 4,100 ten thousand tons.In recent years China PET capacity and output also increases substantially, and within 2010, has reached 2,356 ten thousand tons, becomes world PET and produces, consumes the first big country.
Along with the quick increase of PET output, enter natural pet waste also more and more.The not toxic action of useless PET material itself, but because it has extremely strong unreactiveness, be difficult to by air or microbiological deterioration, and degradation cycle is long under physical environment, although can not produce direct pollution to environment, but along with the increase of usage quantity, pet waste has caused huge environmental pollution.Meanwhile, PET itself is a kind of organic high molecular compound, and the raw material of synthetic PET also derives from the lysate of oil, and the PET plastics that abandon just become the indirect waste of petroleum resources.Using waste polyester as resource, reclaimed, utilized, set up the task of top priority that resource recycling society has become countries in the world efforts at environmental protection.
China polyester reclaims the saving social resources that also do not form in broad sense and the common recognition of environmental protection, and recovery technology is relatively backward, and the exploitation of reclaiming produce market lags behind, and the rate of recovery of domestic polyester bottles is only 6%-10%.Along with increasing rapidly of polyester bottles, polyester film consumption; research and develop energetically polyester recovery technology, process waste polyester oneself through becoming one of key of polyester industrial Sustainable development; reclaiming waste polyester can preserve the ecological environment effectively; can reduce production costs again, realize saving and the regeneration of resource.
The recovery method of PET plastics mainly contains physics absorption method and chemical recycling.Physics absorption method is relatively simple, is mainly the recycle utilization of waste plastic being reprocessed by operations such as cut-out, pulverizing, heat fused, there is no obvious chemical reaction in the course of processing.Although physics recovery technology is saved investment, cost recovery is cheap, but the Performance Ratio novel material of various reprocessed plastic(s) greatly reduces, and contain a large amount of impurity, the use of generally can only demoting, be not suitable for the manufacture of packaging material for food, and it is limited to reclaim the number of times repeating, and finally must seek other way and process.Chemical recycling refers to PET plastics, under the effect of heating and chemical reagent, depolymerization reaction occurs, and is converted into less molecule, intermediate raw material or is converted into monomer.For polyester, chemical recycling can make polyester chain fragment into the ethylene glycol terephthalate that relative molecular mass is lower (BHET) intermediate or degradable for terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG), then after separation, purifying, the monomer of polyester or the raw material of synthetic other Chemicals are produced in conduct again, thereby realize the recycle of resource.At present, chemical recycling exists that cost recovery is high, removal process easily produces secondary pollution problems, only has the chemical recovery technology of research, exploiting economy could effectively promote the regeneration of this resin.Compare with the PET polyester of producing with new raw material, cost recovery at present does not also have competitive power, therefore application not yet on a large scale.
Corn alcohol is as a kind of mixed alcohols that utilizes maize straw degraded to make, it not only can effectively utilize recycling maize straw, reduce burning waste, the atmospheric pollution of rural area maize straw, can also make with lower cost raw material corn alcohol, for the production of unsaturated polyester provides inexpensive raw material; Resinol is the Primary product extracting by sorbyl alcohol catalytic pyrolysis---multicomponent binary alcohol, from bio-based, by formula, regulates, and can directly apply to the production of unsaturated polyester.This patent is on the basis of refinement formulating of recipe, adopt above-mentioned two kinds of polyol blends to carry out alcoholysis to RPET, improve the preparation technology of unsaturated polyester, not only can greatly reduce unsaturated polyester manufacturing cost, and obviously improved in quality multinomial performance, for example, tensile strength and flexural strength etc. are all higher than common product, the Application Areas of having widened RPET and biomass alcohols, further improves the value of recycle.
Summary of the invention
The object of the invention is to select polyol blend is the alcoholysis agent of RPET, carries out the optimization of alcoholysis conditions, utilizes polyol blend degraded RPET under optimal conditions, and carries out the esterification in later stage, prepares unsaturated polyester resin.
Technical scheme of the present invention: production process is divided into two portions, first, utilizes the polyol blend of certain part by weight to carry out alcohols degraded to RPET plastics, obtains alcoholysis product; Then, the reactants such as the alcoholysis product obtaining and phthalic anhydride, cis-butenedioic anhydride and dicyclopentadiene are carried out to esterification polyreaction, and utilize vinylbenzene to carry out dilution process to the product obtaining can to obtain unsaturated polyester resin.
The first step, alcoholysis reaction
The corn alcohol of 500 weight parts is joined in reactor, pass into nitrogen, water coolant is carried out to total reflux simultaneously, be heated with stirring to 80-100 ℃, in reactor, add the zinc acetate catalyst of 0.3 weight part and the RPET plastics of 800 weight parts continuation stirring to be warming up to 180-230 ℃ again, and at 190-240 ℃, be incubated, in reactor, PET all dissolves follow-up continuation of insurance temperature 1-3h, subsequently the temperature of reactor is down to 170-200 ℃.
Second step, esterification polyreaction
Temperature of reaction is reduced to after 130-170 ℃, the phosphoric acid of 0.18 weight part is joined in reactor to insulation 20-50min; Then the phthalic anhydride of the cis-butenedioic anhydride of 50-345 weight part, 20-80 weight part and appropriate dicyclopentadiene are joined in reactor, continuation stirring is warming up to 175-200 ℃ and carries out isothermal reaction, note controlling and heat up in a steamer a temperature, sampling one-shot measurement acid number per hour, reaches below 35mgKOH/g the acid number of reaction mass.
The 3rd step, prepares unsaturated polyester resin solution
After question response completes, reactor is lowered the temperature, add the stopper of 0.02-0.15 weight part and the Diethylene Glycol mixed solution of 1.0-0.5 weight part simultaneously, reactor is cooled to after 100-160 ℃, adds the vinylbenzene of 500-1000 weight part.Fully stir and make vinylbenzene compatible with synthetic unsaturated polyester, continue stirring, reaction system is cooled to below 50 ℃, obtain unsaturated polyester ester solution.
A kind of alcohol mixture alcoholysis RPET resin that utilizes provided by the present invention compared with prior art has the following advantages for the technique of unsaturated polyester resin: with RPET, be raw material production unsaturated polyester resin, can reuse RPET, realizing utility value turns waste into wealth, not only solve problem of environmental pollution, can also bring appreciable economic interests to enterprise; Meanwhile, utilize polyol blend as alcoholysis agent, RPET to be degraded, and then make unsaturated polyester resin, not only can reduce the cost of product, produce larger economic worth, can also promote the suitability for industrialized production of biological alcohols, drive rural economic development.
Embodiment
Below in conjunction with specific embodiment, a kind of alcohol mixture alcoholysis RPET resin that utilizes proposed by the invention is described in further detail for the technique of unsaturated polyester resin:
Embodiment 1
Alcoholysis reaction: add 800g corn alcohol and 200g Diethylene Glycol as alcoholysis agent in reactor, be then warming up to 100 ℃, add 0.94g catalyst acetic acid zinc, and be warming up to 150 ℃.Drop into 1000g RPET plastics, and be incubated 1h after being warming up to 200 ℃, be incubated after 3h that PET dissolves completely after being warming up to afterwards 205 ℃ and still in solution present water white transparency.
Esterification polyreaction: be cooled to 170 ℃ in reactor after alcoholysis completely, add phosphoric acid insulation 20min, then drop into 155g cis-butenedioic anhydride, 63g phthalic anhydride and 150g dicyclopentadiene, and after being risen to 180 ℃, reactor temperature is incubated 1h, be warming up to subsequently 200 ℃, insulation 3h is less than 40mgKOH/g to acid number.
Vinylbenzene diluting reaction: when polymkeric substance acid number reaches 40mgKOH/g, in reactor, add 0.112g stopper, reactor stirs and is cooled to 120 ℃, the vinylbenzene mixed solution that adds subsequently 815g, continue to stir and be cooled to 50 ℃, solution in reactor is shifted out, obtain unsaturated polyester resin.Viscosity is 150mPas.After solidifying, the tensile strength of product reaches 81.6MPa.
Embodiment 2
Alcoholysis reaction: in reactor, add 800g corn alcohol and and 100g glycerol as alcoholysis agent, be then warming up to 100 ℃, add 0.86g catalyst acetic acid zinc, and be warming up to 150 ℃.After dropping into 950g RPET polyester and being warming up to 190 ℃, be incubated 1h, be incubated after 3h that PET dissolves completely after being warming up to afterwards 205 ℃ and still in solution present water white transparency.
Esterification polyreaction: be cooled to 170 ℃ in reactor after alcoholysis completely, add phosphoric acid insulation 20min, then drop into 155g cis-butenedioic anhydride, 63g phthalic anhydride and 150g dicyclopentadiene, and after being risen to 180 ℃, reactor temperature is incubated 1h, be warming up to subsequently 200 ℃, insulation 3h is less than 40mgKOH/g to acid number.
Vinylbenzene diluting reaction: when polymkeric substance acid number reaches 40mgKOH/g, in reactor, add 0.112g stopper, reactor stirs and is cooled to 120 ℃, the vinylbenzene mixed solution that adds subsequently 845g, continue to stir and be cooled to 50 ℃, solution in reactor is shifted out, obtain unsaturated polyester resin.Viscosity is 165mPas.After after solidifying, the tensile strength of product reaches 84.7MPa.
Embodiment 3
Alcoholysis reaction: add 400g corn alcohol, 400g resinol, 200g Diethylene Glycol and 150g glycerol as alcoholysis agent in reactor, be then warming up to 100 ℃, add 0.84g catalyst acetic acid zinc, and be warming up to 150 ℃.Drop into 950g RPET plastics, and be incubated 1h after being warming up to 200 ℃, be incubated after 3h that PET dissolves completely after being warming up to afterwards 205 ℃ and still in solution present water white transparency.
Esterification polyreaction: be cooled to 170 ℃ in reactor after alcoholysis completely, add phosphoric acid insulation 20min, then drop into 105g cis-butenedioic anhydride, 23g phthalic anhydride and 165g dicyclopentadiene, and after being risen to 180 ℃, reactor temperature is incubated 1h, be warming up to subsequently 200 ℃, insulation 3h is less than 40mgKOH/g to acid number.
Vinylbenzene diluting reaction: when polymkeric substance acid number reaches 40mgKOH/g, in reactor, add 0.202g stopper, reactor stirs and is cooled to 120 ℃, the vinylbenzene mixed solution that adds subsequently 875g, continue to stir and be cooled to 50 ℃, solution in reactor is shifted out, obtain unsaturated polyester resin.Viscosity is 180mPas.After solidifying, the tensile strength of product reaches 80.3MPa.
Embodiment 4
Alcoholysis reaction: add 800g corn alcohol and 560g resinol as alcoholysis agent in reactor, be then warming up to 100 ℃, add 0.66g catalyst acetic acid zinc, and be warming up to 150 ℃.After dropping into 920g RPET polyester and being warming up to 200 ℃, be incubated 1h, be incubated after 3h that PET dissolves completely after being warming up to afterwards 205 ℃ and still in solution present water white transparency.
Esterification polyreaction: be cooled to 170 ℃ in reactor after alcoholysis completely, add phosphoric acid insulation 20min, then drop into 185g cis-butenedioic anhydride, 13g phthalic anhydride and 105g dicyclopentadiene, and after being risen to 180 ℃, reactor temperature is incubated 1h, be warming up to subsequently 200 ℃, insulation 3h is less than 40mgKOH/g to acid number.
Vinylbenzene diluting reaction: when polymkeric substance acid number reaches 40mgKOH/g, in reactor, add 0.135g stopper, reactor stirs and is cooled to 120 ℃, the vinylbenzene mixed solution that adds subsequently 965g, continue to stir and be cooled to 50 ℃, solution in reactor is shifted out, obtain unsaturated polyester resin.Viscosity is 167mPas.After solidifying, product tensile strength reaches 79.8MPa.
Claims (3)
1. the technique of utilizing the synthetic unsaturated polyester resin of alcohol mixture alcoholysis RPET plastics, is characterized in that: comprise the following steps:
The first step, alcoholysis reaction
The corn alcohol of 500 weight parts is joined in reactor, pass into nitrogen, water coolant is carried out to total reflux simultaneously, be heated with stirring to 80-100 ℃, in reactor, add the zinc acetate catalyst of 0.3 weight part and the RPET plastics of 800 weight parts continuation stirring to be warming up to 180-230 ℃ again, and at 190-240 ℃, be incubated, in reactor, PET all dissolves follow-up continuation of insurance temperature 1-3h, subsequently the temperature of reactor is down to 170-200 ℃;
Second step, esterification polyreaction
Temperature of reaction is reduced to after 130-170 ℃, the phosphoric acid of 0.18 weight part is joined in reactor to insulation 20-50min; Then the phthalic anhydride of the cis-butenedioic anhydride of 50-345 weight part, 20-80 weight part and appropriate dicyclopentadiene are joined in reactor, continuation stirring is warming up to 175-200 ℃ and carries out isothermal reaction, note controlling and heat up in a steamer a temperature, sampling one-shot measurement acid number per hour, reaches below 35mgKOH/g the acid number of reaction mass;
The 3rd step, prepares unsaturated polyester resin solution
After question response completes, reactor is lowered the temperature, add the stopper of 0.02-0.15 weight part and the Diethylene Glycol mixed solution of 1.0-0.5 weight part simultaneously, reactor is cooled to after 100-160 ℃, adds the vinylbenzene of 500-1000 weight part.Fully stir and make vinylbenzene compatible with synthetic unsaturated polyester, continue stirring, reaction system is cooled to below 50 ℃, obtain unsaturated polyester ester solution.
2. the alcohol mixture alcoholysis RPET resin that utilizes as claimed in claim 1, for the technique of unsaturated polyester resin, is characterized in that: in described alcoholysis reaction process, alcoholysis agent used is the polyol blends such as corn alcohol, resinol.
3. the alcohol mixture alcoholysis RPET resin that utilizes as claimed in claim 1 is for the technique of unsaturated polyester resin, it is characterized in that: in described esterification-polymerization process, adding reactant is cis-butenedioic anhydride, phthalic anhydride and dicyclopentadiene etc., and its reaction conditions is 175-200 ℃ of isothermal reaction 3-5h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367769A (en) * | 2015-12-17 | 2016-03-02 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing PET |
| CN107840947A (en) * | 2017-11-16 | 2018-03-27 | 厦门市五翔盛环保科技有限公司 | A kind of method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material |
| CN111647147A (en) * | 2020-06-18 | 2020-09-11 | 福建师范大学 | Method for preparing fiber source unsaturated polyester resin by taking waste polyester textile fabric as raw material |
-
2013
- 2013-11-08 CN CN201310556734.3A patent/CN103554380A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367769A (en) * | 2015-12-17 | 2016-03-02 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing PET |
| CN105367769B (en) * | 2015-12-17 | 2017-05-31 | 肇庆福田化学工业有限公司 | A kind of utilization PET synthesizes the method for unsaturated polyester resin |
| CN107840947A (en) * | 2017-11-16 | 2018-03-27 | 厦门市五翔盛环保科技有限公司 | A kind of method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material |
| CN111647147A (en) * | 2020-06-18 | 2020-09-11 | 福建师范大学 | Method for preparing fiber source unsaturated polyester resin by taking waste polyester textile fabric as raw material |
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Application publication date: 20140205 |