CN101343356A - Method for modifying waste and old polyester plastics with sulfonation - Google Patents
Method for modifying waste and old polyester plastics with sulfonation Download PDFInfo
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- CN101343356A CN101343356A CNA2008100226515A CN200810022651A CN101343356A CN 101343356 A CN101343356 A CN 101343356A CN A2008100226515 A CNA2008100226515 A CN A2008100226515A CN 200810022651 A CN200810022651 A CN 200810022651A CN 101343356 A CN101343356 A CN 101343356A
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Abstract
The invention relates to a method for modifying the waste polyester plastics by sulphonation, which comprises the steps that recycled polyester plastics (polyethylene terephthalate (PET) / polycarbonate (PC)) is converted into the renewable resource through chemical modification, thus not only the environmental contamination can be lessened, but also the method conforms to the developing trend of the conservation-oriented society. The waste polyester high molecular material the origin of which is wide is selected to induct the sulfonate group as the hydrophilic group on the main chain through sulphonation reaction, thereby the surface activating agent of an amphiphathic molecule structure is constituted. A series of high polymers with different sulfonating degrees can be obtained through changing the reaction time, reaction temperature and the dosage of the sulphonating agent in the method. The material origins the sulfonated bodies of the invention are wide, the price is low, the application is wide, the route of the manufacturing technique is simple, thereby the sulfonated bodies are sulfonation high polymer with promising future.
Description
Technical field
The invention belongs to the junk manufacture field, relate to a kind of preparation method who utilizes the waste and old polyester plastics sulfonation modifying to become sulfonated high polymer.
Background technology
Polyethylene terephthalate (PET) plastics have in packaging field widely to be used, and no matter is packing film, coiled material, or some daily living articles, all uses the PET plastics.Polycarbonate (PC) resin is a kind of thermoplastic engineering plastic of excellent property, has outstanding impact resistance, anti-creep and dimensional stability are good, heat-resisting, water-intake rate is low, nontoxic, dielectric properties are good, being unique product with good transparency in the five large-engineering plastics, also is the fastest general engineering plastic of growth in recent years.Be widely used in fields such as automobile, electric, building, office equipment, packing, sports equipment, health care at present,, be extended to high-tech areas such as aerospace, computer, CD just rapidly along with deepening continuously of study on the modification.The present PET of China, PC plastics consumption are very high, and the regeneration of waste PET, PC not only can reduce environmental pollution, and can turn waste into wealth.Part is utilized but have only seldom at present, and remaining is arbitrarily abandoned, and causes the waste and the environmental pollution of resource.With the PET that reclaims, PC reprocessing is handled and is made it become renewable resources by chemical modification, not only can alleviate environmental pollution, and be the development trend of conservation-minded society.Because the polyester macromolecular material has the excellent comprehensive performance, its good thermotolerance and mechanical system can be subjected to extensive concern.Sulfonic acid group is incorporated in the polyester macromolecule main chain, promptly can keeps the excellent properties of polyester macromolecule, can bring into play the characteristics of sulfonic group base polymer again.
As effective stain remover, sulfonated polyester compounds comes into one's own day by day.For example, United States Patent (USP) 3557039 discloses a kind of stable aqueous dispersions, it comprises water and crystallizable block of water-insoluble or graftomer, it contains and has poly-(ethylene diester) segment of the unitary linearity of enough ethylene glycol terephthalates, and these polymkeric substance are by monomer sodiosulfoisophthalic acid second diester prepared in reaction.United States Patent (USP) 5,599,782 disclose the sulfonated polyester compounds that uses as stain remover.The polymerisable monomer of mentioning in the document comprises ,-sodium sulfonate for phenylformic acid, sodium sulfonate for dimethyl isophthalate, dimethyl terephthalate (DMT), terephthalic acid and ethylene glycol.The method that Chinese patent 00816618.8 discloses sulfonated polyester compounds is with sulfonated acid or ester and hydroxy-containing compounds reaction, form sulfonation hydroxyl end groups ester, make its polyester carry out transesterification reaction then, form required sulfonated polyester compounds with aftercondensated with poly-(ethylene glycol terephthalate) base.
The conventional production methods existing problems of the sulfonated polyester compounds that uses as stain remover and textiles sizing agent, reason is that these methods have comprised expensive starting raw material, the tediously long process-cycle.The preparation of above sulfonated polyester compounds all is an earlier sulfonation monomer repolymerization, the present invention utilize waste and old polyester material sulfonation modifying be by polymeric superpolymer again sulfonation not only can alleviate environmental pollution, turn waste into wealth, social resources have been saved, advantages such as and production technique is simple, and the process-cycle is short.
Summary of the invention
Technical problem: the objective of the invention is to study provides a kind of method of utilizing the waste and old polyester plastics modifying waste and old polyester plastics with sulfonation, and this method can obtain the superpolymer of a series of different sulfonation degree.
Technical scheme: the preparation method of modifying waste and old polyester plastics with sulfonation of the present invention is as follows:
A. get waste and old polyester plastics and be dissolved in organic solvent, be stirred to dissolving fully;
B. in containing the organic solvent of waste and old polyester plastics, drip sulphonating agent solution, the control rate of addition in 2/min～10 droplet/min; The dropping time is controlled to be 2h～8h; Controlled temperature drips off and continues reaction at 20 ℃～100 ℃;
C. reaction is adjusted to neutrality with basic solution, suction filtration, drying after finishing.
Described waste and old polyester plastics is one or more of polyethylene terephthalate, polycarbonate.
Described sulphonating agent contains sulfonic acid.Sulphonating agent is selected from chlorsulfonic acid, one or more of the oleum or the vitriol oil.Described sulphonating agent is the mixing solutions of the 50wt% oleum and the 98wt% vitriol oil; Volume ratio is 1: 1～10: 1.
Described organic solvent is selected from one or more in methylene dichloride, ethylene dichloride, chloroform, tetrachloroethane, the sherwood oil.
Described basic solution is selected from one or more in sodium hydroxide, potassium hydroxide, the calcium hydroxide.
Drying means is that the sulfonated superpolymer is placed on drying in the vacuum drying oven, and temperature is controlled at 30 ℃～60 ℃.
Beneficial effect: the polyester plastics that is dissolved in organic solvent in the method for the invention generates the faint yellow solid that is insoluble to this organic solvent through sulfonation.Phenomenon is obvious, can well prove to have generated a kind of new sulfonated high polymer.Prepare the degraded that sulfonated high polymer can be avoided superpolymer with this method, prevent phenomenons such as carbonization.
Embodiment
Get waste and old polyester plastics and be dissolved in organic solvent, be stirred to dissolving fully;
Drip sulphonating agent solution in containing the organic solvent of waste and old polyester plastics, control rate of addition and dropping time, heating simultaneously drips off and continues stoichiometric number hour;
Reaction finishes the back and is adjusted to neutrality with basic solution, suction filtration, drying.
Wherein, described waste and old polyester plastics is one or more of polyethylene terephthalate, polycarbonate.
Described sulphonating agent contains sulfuric acid, be preferably selected from chlorsulfonic acid, one or more of the oleum or the vitriol oil, the mixing solutions of the oleum (50wt%) and the vitriol oil (98wt%) more preferably, in this mixing solutions, the volume ratio of the oleum (50wt%) and the vitriol oil (98wt%) is 1: 1～10: 1.
Organic solvent is one or more in methylene dichloride, ethylene dichloride, chloroform, tetrachloroethane, the sherwood oil.
During sulfonation reaction, temperature is controlled at 20 ℃～100 ℃.
The control rate of addition in 2/min～10 droplet/min.
The control dropping time is 2h～8h.
Described basic solution is selected from sodium hydroxide, potassium hydroxide, one or more of calcium hydroxide.
Drying means is that the sulfonated superpolymer is placed on drying in the vacuum drying oven, and temperature is controlled at 30 ℃～60 ℃.
Below in conjunction with embodiment, further specify concrete composition of raw materials and technical process that the present invention utilizes waste and old polyester material preparation sulfonated high polymer.
Embodiment 1:
Configuration oleum (50wt%) and the vitriol oil (98wt%) volume ratio are 3: 1 mixing solutions 10ml.To reflux condensing tube is housed, thermometer adds the methylene dichloride of 50ml in the churned mechanically 100ml three-necked bottle, get 10 gram PC and add in the three-necked bottles, is stirred to dissolving fully.The CH that contains PC
2CL
2Drip the sulfonation solution of preparation in the solution, the control rate of addition be 30 seconds every, the dropping time is 4h, 40 ℃ of reacting by heating temperature drip off and continue reaction 4h.Surveying its sulfonation degree with standard N aOH titration after reaction finishes is 30.15%.
Embodiment 2:
Measure oleum solution 10ml.To reflux condensing tube is housed, thermometer adds the vitriol oil of 20ml in the churned mechanically 100ml three-necked bottle, get 10 gram PET and add in the three-necked bottles, is stirred to dissolving fully.Contain and drip oleum solution in the concentrated sulfuric acid solution of PET, the control rate of addition be 30 seconds every, the dropping time is 4h, 40 ℃ of reacting by heating temperature drip off and continue reaction 6h.Surveying its sulfonation degree with standard N aOH titration after reaction finishes is 33.21%.
Embodiment 3:
Measure chlorosulfonic acid solution 10ml.To reflux condensing tube is housed, thermometer adds the methylene dichloride of 50ml in the churned mechanically 100ml three-necked bottle, get 10 gram PC and add in the three-necked bottles, is stirred to dissolving fully.The CH that contains PC
2CL
2Drip chlorosulfonic acid solution in the solution, the control rate of addition be 30 seconds every, the dropping time is 4h, 40 ℃ of reacting by heating temperature drip off and continue reaction 8h.Surveying its sulfonation degree with standard N aOH titration after reaction finishes is 35.62%.
Products therefrom of the present invention and its esters can be used for: anion surfactant, Zeo-karb, cement water reducing agent, stain remover etc.
Claims (8)
1, a kind of method of modifying waste and old polyester plastics with sulfonation is characterized in that this method is as follows:
A. get waste and old polyester plastics and be dissolved in organic solvent, be stirred to dissolving fully;
B. in containing the organic solvent of waste and old polyester plastics, drip sulphonating agent solution, the control rate of addition in 2/min～10 droplet/min; The dropping time is controlled to be 2h～8h; Controlled temperature drips off and continues reaction at 20 ℃～100 ℃;
C. reaction is adjusted to neutrality with basic solution, suction filtration, drying after finishing.
2, the method for modifying waste and old polyester plastics with sulfonation according to claim 1 is characterized in that described waste and old polyester plastics is one or more of polyethylene terephthalate, polycarbonate.
3, the method for modifying waste and old polyester plastics with sulfonation according to claim 1 is characterized in that, described sulphonating agent contains sulfonate radical.
4, the method for modifying waste and old polyester plastics with sulfonation according to claim 1 is characterized in that, described sulphonating agent is selected from chlorsulfonic acid, one or more of the oleum or the vitriol oil.
5, the method for modifying waste and old polyester plastics with sulfonation according to claim 4 is characterized in that, described sulphonating agent is the mixing solutions of the 50wt% oleum and the 98wt% vitriol oil; Volume ratio is 1: 1～10: 1.
6, the method for modifying waste and old polyester plastics with sulfonation according to claim 1 is characterized in that described organic solvent is selected from one or more in methylene dichloride, ethylene dichloride, chloroform, tetrachloroethane, the sherwood oil.
7, the method for modifying waste and old polyester plastics with sulfonation according to claim 1 is characterized in that, described basic solution is selected from one or more in sodium hydroxide, potassium hydroxide, the calcium hydroxide.
8, the method for modifying waste and old polyester plastics with sulfonation according to claim 1 is characterized in that, drying means is that the sulfonated superpolymer is placed on drying in the vacuum drying oven, and temperature is controlled at 30 ℃～60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100226515A CN101343356A (en) | 2008-07-18 | 2008-07-18 | Method for modifying waste and old polyester plastics with sulfonation |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100226515A CN101343356A (en) | 2008-07-18 | 2008-07-18 | Method for modifying waste and old polyester plastics with sulfonation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955581A (en) * | 2010-10-10 | 2011-01-26 | 四川宏扬高分子科技有限公司 | Water-soluble polyester slurry prepared from waste polyester plastics and preparation method thereof |
| CN108556186A (en) * | 2018-04-13 | 2018-09-21 | 佛山市罟特化工贸易有限公司 | A kind of integrated conduct method of polyurethane waste material |
| CN111004479A (en) * | 2019-11-14 | 2020-04-14 | 苏州市新广益电子有限公司 | PBT/PVDF composite membrane and production process thereof |
| CN111116914A (en) * | 2019-12-26 | 2020-05-08 | 白银图微新材料科技有限公司 | Synthesis method for preparing sulfonated poly (amino) sulfate by using poly (amino) sulfate polymer as raw material |
-
2008
- 2008-07-18 CN CNA2008100226515A patent/CN101343356A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955581A (en) * | 2010-10-10 | 2011-01-26 | 四川宏扬高分子科技有限公司 | Water-soluble polyester slurry prepared from waste polyester plastics and preparation method thereof |
| CN108556186A (en) * | 2018-04-13 | 2018-09-21 | 佛山市罟特化工贸易有限公司 | A kind of integrated conduct method of polyurethane waste material |
| CN111004479A (en) * | 2019-11-14 | 2020-04-14 | 苏州市新广益电子有限公司 | PBT/PVDF composite membrane and production process thereof |
| CN111116914A (en) * | 2019-12-26 | 2020-05-08 | 白银图微新材料科技有限公司 | Synthesis method for preparing sulfonated poly (amino) sulfate by using poly (amino) sulfate polymer as raw material |
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Open date: 20090114 |