CN104327259B - A kind of preparation method of low melting point regeneration copolyesters - Google Patents
A kind of preparation method of low melting point regeneration copolyesters Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to the preparation method of a kind of low melting point regeneration copolyesters, for chemical regeneration and the polyester functionalization development field of waste and old polyester, adopt a kind of binary titanium alkoxide alkali metal coordination compound being dissolvable in water ethylene glycol as catalyzer, the copolycondensation process of the ethylene glycol depolymerization of catalysis waste and old polyester material and depolymerization product and aliphatic dibasic acid small molecules polyether ester compound, and melting range can be obtained at 110-210 DEG C, melting range is less than 40 DEG C, coloury crystallinity low melting point regeneration copolyesters.The catalyzer that present method adopts all has higher catalytic activity for the ethylene glycol depolymerization of polyester and depolymerization product copolymerization process, just copolymerization is again can be used for without the need to being removed from depolymerization product by catalyzer, greatly can save depolymerization product separating-purifying cost, enhance productivity, for the material continuous functionalization chemical regeneration of waste and old polyester provides possibility.
Description
Technical field
The invention belongs to the chemical regeneration technical field of polyester, relate to the preparation method of a kind of low melting point regeneration copolyesters, particularly relate to binary titanium alkoxide alkali metal coordination compound that a kind of employing is dissolvable in water ethylene glycol prepares low melting point regeneration copolyesters for the ethylene glycol depolymerization of catalyst, polyester and depolymerization product copolymerization method as catalyzer.
Background technology
Polyethylene terephthalate (polyethyleneterephthalate, PET, be called for short polyester) be a kind of semi-crystalline thermoplastic macromolecule material of excellent performance, be widely used in the fields such as chemical fibre, packaging, medicine, electric mechanical, 2010, global polyester ultimate production reached 5,610 ten thousand tons.While PET industry develop rapidly, polyester product performance process problem that is single and waste and old polyester goods is comed one after another, for the pressure that the huge storage alleviating waste polyester goods brings to resource environment, meet market for functionalized polyester materials demand simultaneously, the functionalization regeneration of waste polyester goods is achieved many things at one stroke beyond doubt.
In conjunction with the physicochemical characteristic of polyester, its way of recycling is mainly divided into physics to regenerate and chemical regeneration two kinds.Physics method of reproduction is based on the thermoplasticity of polyester, by the method for carrying out melting granulation again after the removal of impurities of waste and old polyester goods, cleaning, pulverizing drying being realized the regeneration of polyester, although physics regeneration has, cost is low, the simple feature of technology, but the degradation that only can realize polyester reclaims, and recovered frequency is limited, enclosed circulation can not be realized.The reversibility of chemical regeneration based on polyester polycondensation reaction and the nucleophilic reaction mechanism of transesterification reaction, polyester is made to be depolymerized to polymerization single polymerization monomer or intermediate by the attack of small molecules depolymerizing agent to macromolecular chain, after separating-purifying, carry out repolymerization realize regeneration, main depolymerization method has hydrolysis, methyl alcohol solution and ethylene glycol solution three kinds, wherein hydrolysis reaction needs acid or the alkali of high density, methyl alcohol solution reaction needed high temperature and high pressure environment, therefore high to equipment requirements, industrialization difficulty is large; By contrast, it is gentleer that ethylene glycol solution has reaction conditions, and can utilize existing polyester production facility, technical process is short, is easy to realize continuous prodution, the feature that easier functionalization regeneration etc. are outstanding and enjoy industry to favor.Meanwhile, in order to expand the Application Areas of recycled polyester goods, promote the added value of reconstituted product, the functional modification of recycled polyester has also become the importance paid close attention in polyester chemistry regenerative process.Current low-melting point polyester has broad application prospects and demand in non-woven industry as outstanding hot-melt adhesive material, is therefore also a Main way of functionalized polyester exploitation.
The ethylene glycol solution of PET reacts the heterogeneous reaction of normal pressure or the low pressure of normally carrying out at 180-220 DEG C.Because temperature of reaction is higher, in order to prevent the reaction times long generation causing the side reactions such as the decomposition of polymer degradation, depolymerization product and glycol ether generation, usually need to add alcoholysis catalysts accelerated reaction.At present, the alcoholysis catalysts known the most take zinc acetate as the metallic salt of representative, although the alcoholysis catalytic efficiency of zinc acetate is high, but zinc acetate also exists serious defect as depolymerization catalyst, first its consumption is higher, be generally the 0.5-1.5% of PET quality, and be difficult to after depolymerization remove from product, the zine ion simultaneously remaining in high-content in depolymerization product can accelerate because it comprehends to the catalytic machine of ketonic oxygen coordination side reactions such as causing in repolymerization process thermal destruction, molecular weight is increased limited, the viscosity of recycled polyester is low, poor quality.Patent of invention CN102584594ACoCl
4 2-/ NiCl
4 2-the method of the ionic liquid-catalyzed alcoholysis polyethylene terephthalate of type, patent of invention CN102731310A the first transition metal ion liquid catalyst alcoholysis ethylene glycol terephthalate method, and CN200810101969.2 is used in the polyester alcoholysis catalysts announced in the catalyzer of alcoholysis polyethylene terephthalate, although have reaction conditions gentleness, speed of response is fast, transformation efficiency is high, catalytic selectivity is high, the advantages such as catalyzer can be recycled, but the defect that existence one is very important simultaneously, be exactly in the catalyzer of this type of ionic liquid haloid element content very high, if fail catalyzer to remove from depolymerization product, then can cause macromolecular decomposition because producing hydrogen halide in repolymerization process, have a strong impact on the quality of repolymerization goods, and catalyzer removal thoroughly from depolymerization product significantly will be increased production cost, lose more than gain.Patent of invention CN200810126347.5SO
4 2-/ MO
2type solid super acid catalyst degraded polyethylene terephthalate prepares a kind of SO disclosed in BHET (bishydroxyethyl terephthalate)
4 2-/ MO
2although it is easily separated that type solid acid catalyst has product, catalytic selectivity is high, the feature easily recycled, and because it is heterogeneous catalyst, in catalytic reaction, mass transfer process is complicated, causes catalytic efficiency lower.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of low melting point regeneration copolyesters, be intended to solve the published alcoholysis catalysts that uses in the current polyesterols solution functionalization chemical regeneration process residual disadvantageous effect to producing in polymerization process again in alcoholysis product, and the problem causing catalytic efficiency low due to the heterogeneous property of catalyzer in depolymerization liquid.The preparation method adopting low melting point provided by the invention to regenerate copolyesters just can be used for copolymerization again without the need to being removed from depolymerization product by catalyzer, greatly can save depolymerization product separating-purifying cost, ensure that repolymerization process carry out smoothly and low melting point regeneration copolyesters quality, for the efficiently high-quality functionalization chemical regeneration of waste and old polyester goods provides possibility.
The alcoholysis of PET polyester and this Liang Zhong reacting quintessence of polycondensation are all realize molecule chain break with the dimolecular reaction mechanism of acyl-oxygen cleavage and increase, but because the factor difference such as reactant nature and reaction conditions of alcoholysis reaction and polycondensation is larger, have not yet to see a kind of catalyzer can all realize reaction efficiently and directionally in two simultaneously catalysis under reaction conditions, depolymerization catalyst often has a negative impact to polycondensation process, as serious thermal destruction catalysis etc. simultaneously.Therefore need in PET polyester chemistry regenerative process at present the catalyzer removing that alcoholysis process used to ensure depolymerization product the carrying out smoothly of polymerization process again, this process significantly will add cost of withdrawing deposit, and make PET polyester chemical regeneration and chemistry functional regeneration Difficulty.The present invention is by adopting bimetal matching structure design, catalyzer is made to combine two kinds of catalytic mechanisms of the dimolecular reaction of acyl-oxygen cleavage, i.e. ligand exchange mechanism and metal alkoxide mechanism, this catalyzer all can be shown efficiently and the catalytic activity of orientation in the alcoholysis and polycondensation two kinds reaction of PET, and side reaction is few, the catalyzer of this bimetal fit structure provided by the invention is ate complex, suitable and the rational transition metal titanium of outer shell electron distribution of preferred electronegativity is as the central atom of acid group coordination ion, make part with di-alcohols structure and promote homogeneity and ligand exchange activity, adopt basic metal race as positively charged ion on the one hand for promoting the ligancy of catalytic center titanium atom, part is made more easily deformation to occur, thus strengthen the catalytic activity of titanium in alcoholysis and polycondensation process, on the other hand, basic metal race positively charged ion can realize auxiliary acceleration by the mode forming metal alkoxide to alcoholysis reaction, all high reactivity can be shown to PET depolymerization and copolycondensation to reach this catalyzer, without the need to being removed after depolymerization, therefore low melting point regeneration copolyesters preparation method provided by the invention can effectively solve foregoing problem.
The preparation method of a kind of low melting point regeneration copolyesters of the present invention, comprises the following steps:
1) ethylene glycol depolymerization is carried out to PET polyester:
1.1) alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is dissolved in depolymerizing agent ethylene glycol, forms depolymerization solution;
1.2) depolymerization solution is mixed with PET polyester and stirred carry out depolymerization reaction, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4-50:1, and depolymerization reaction temperature is 160-240 DEG C, and reaction system pressure is 1-2.5atm, and the reaction times is 30min-8h;
The structural formula of described alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is:
Wherein, M
+being IA race metallic cation, is Li
+, Na
+, K
+or Rb
+;
R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4,
This kind of structure design has following advantage:
A)-O-R '-O-structure can make this Titanium series catalyst have solubility in depolymerizing agent ethylene glycol, to guarantee that depolymehzation process is for homogeneous catalysis, promotes catalytic efficiency;
B) M
+the introducing of IA race metallic cation can effectively avoid Ti with-(-O-R '-O-)-
3the catalytic activity that the chain-like structure that structure autohemagglutination forms one dimension prolongation causes reduces;
C) M
+the introducing of IA race metallic cation can make the ligancy of Ti atom in catalyzer improve, thus cause the stability of catalyst space structure to reduce, there is ligand exchange reaction due to coordination in the ester bond more easily and in depolymerizing agent and polyester, thus causes macromole chain rupture.Meanwhile, the coordination of Ti and ester bond can increase the Electron Affinities of carbonyl carbon in macromolecular chain, and M
+can have an effect with the hydroxyl in depolymerizing agent ethylene glycol and the nucleophilicity of hydroxyl oxygen, therefore Ti and M can be increased
+the mutual promoting action of both makes at the easier attack polyester macromolecule of ethylene glycol and acyl-oxygen bond rupture occurs, i.e. the alcoholysis of PET, therefore has very high alcoholysis catalytic activity;
D) high in temperature of reaction, reactant is mainly in the polycondensation process of polyester oligomer, and the titanium ethylene glycolate acid group part of this catalyzer can make still have efficient catalytic activity in its polycondensation process by ligand exchange effect.
2) to decolouring and the purification of depolymerization product, step is as follows:
2.1) in step 1) to add containing quality of activated carbon mark in gained solution be the ethylene glycol dispersion liquid of 0.5-5%, at temperature is 150-220 DEG C, atmospheric pressure reflux stirs decolouring 1-5h;
2.2) gac of impurity and decolouring is then removed after filtration;
2.3) repeating step 2.1) and 2.2) 2-5 time, also namely decolouring and filtration procedure carry out 2-5 time repeatedly, obtain the ethylene glycol solution of the depolymerizing substance after removal of impurities decolouring;
2.4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 190-210 DEG C and pressure is 0.5-0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
3) copolymerization of depolymerization product, concrete step is as follows:
3.1) preparation of modification by copolymerization carboxylate: by binary of fatty acids, ethylene glycol, small molecules polyethers three with etc. amount mixing, and to add a certain amount of titanium ethylene glycolate alkali metal complex be catalyzer, be 150-170 DEG C in temperature of reaction, pressure is carry out esterification 2-3h under 1atm, distillates the water generated in reaction process in time simultaneously, protect with rare gas element in reaction process, reaction terminates rear acquisition aliphatic dibasic acid small molecules polyether ester compound;
3.2) by step 3.1) and step 2) the aliphatic dibasic acid small molecules polyether ester compound that obtains and purification and the depolymerization product after decolouring, polycondensation catalyst and thermo-stabilizer, be 1atm at 180-220 DEG C and pressure, under protection of inert gas, be uniformly mixed by certain mass ratio;
3.3) then, temperature of reaction is increased to 220-240 DEG C, continue reaction 60-120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa;
3.4) then, temperature of reaction is increased to 265-290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 100-180min, namely obtain low melting point regeneration copolyesters.
As preferred technical scheme:
The preparation method of a kind of low melting point regeneration copolyesters as above, the molar mass of PET polyester calculates with 192g/mol, the preferred 8-20:1 of mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester, too much ethylene glycol can cause the side reaction generating glycol ether to occur, the very few productive rate that will reduce depolymerization speed and monomer, the preferred 180-210 DEG C of depolymerization reaction temperature, temperature of reaction is too low can reduce depolymerization rate, too high, can cause the generation of side reaction; In described depolymerization solution, the consumption of described binary titanium alkoxide alkali metal coordination compound is the 0.1%-1% of quality of glycol; Stir during described depolymerization reaction, stir speed (S.S.) is that 50-1500 turns/min; Described depolymerization reaction carries out under protection of inert gas.
The preparation method of a kind of low melting point regeneration copolyesters as above, described binary titanium alkoxide alkali metal coordination compound is obtained by following steps:
A) by general formula be Ti (OR)
4titanium compound under 50-150 DEG C and nitrogen protection condition, be dibasic alcohol the HO-R '-OH Homogeneous phase mixing of 2-4 with carbonatoms; Wherein, the saturated hydrocarbon chains structure of R to be carbonatoms be 2-4, R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4; In conjunction with building-up reactions activity, catalytic activity, raw material stability and price factor, Ti (OR)
4preferred tetrabutyl titanate, titanium isopropylate; The preferred ethylene glycol of dibasic alcohol, 1,2-PD;
B) add IA race metal hydroxides MOH, continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180-250 DEG C;
C) in reaction process, backflow dibasic alcohol also gets rid of the lower boiling monohydroxy-alcohol R-OH and water that react and generate, and the reaction times is 2-5 hour, and reaction terminates rear fast by the dibasic alcohol evaporation acquisition white completely in system or micro-yellow solid;
D) utilized by above-mentioned solid ethanol-Gossypol recrystallized from chloroform repeatedly to obtain colourless or light yellow crystal and be described binary titanium alkoxide alkali metal coordination compound.
The preparation method of a kind of low melting point regeneration copolyesters as above, Ti (OR)
4be 1:20-100 with the mol ratio of HO-R '-OH; MOH and Ti (OR)
4mol ratio be 2.01-2.05:1; Step c) in, describedly refer to that, at temperature is 190-210 DEG C, reaction system pressure is under 0.5-0.8atm fast, in 0.5-5min by dibasic alcohol evaporation in system completely.
The preparation method of a kind of low melting point regeneration copolyesters as above, described PET polyester is for being any type of goods made by polyethylene terephthalate and waste and old product by composition.
The preparation method of a kind of low melting point regeneration copolyesters as above, the decolouring of described depolymerization product and the step of purification, step 2.1) in, the add-on of the ethylene glycol solution containing gac is 0.5-5 times of depolymerizing substance ethylene glycol solution quality.
The preparation method of a kind of low melting point regeneration copolyesters as above, step 3.1) in, described binary of fatty acids is 1,6-hexanodioic acid, one or more in 1,10-sebacic acid; Described small molecules polyethers for being polymerized to glycol ether, Triethylene glycol, one or more in tetraethylene-glycol; The add-on of described titanium ethylene glycolate alkali metal complex is 50-100ppm, and stir speed (S.S.) is 50-100rpm; Step 3.2) in, described presses certain mass than mixing, and namely the mass ratio of depolymerization product and aliphatic dibasic acid small molecules polyether ester compound is 9:1-1:2; Described polycondensation catalyst is one or more in binary titanium alkoxide alkali metal coordination compound catalyzer, antimony glycol, antimony acetate, antimonous oxide, Germanium tetraacetate, germanium dioxide, titanium isopropylate, tetra-n-butyl titanate, titanium ethylene glycolate; The add-on of described polycondensation catalyst is the 0-200ppm of the depolymerization product quality after purifying and decolouring; Described thermo-stabilizer is one or more in trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, primary ammonium phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate etc.; The add-on of described thermo-stabilizer is the 50ppm-500ppm of the depolymerization product quality after purifying and decolouring.
The preparation method of a kind of low melting point regeneration copolyesters as above, step 3.2) in, be uniformly mixed and refer to that mixing speed is that 50-80 turns/min, be uniformly mixed 30-60min; Step 3.3) in, at the uniform velocity reduction pressure is 0.5kPa-10kPa/min to the air pressure changing down of 1kPa, and need during reaction to stir, mixing speed is that 50-80 turns/min; Step 3.4) in, continuing at the uniform velocity to reduce pressure to the air pressure changing down of 20Pa is 100Pa-1kPa/min, and continues when reacting to stir, and mixing speed is that 80-120 turns/min.
Beneficial effect:
(1) preparation method of a kind of low melting point regeneration copolyesters of the present invention belongs to the high-valued regeneration to waste and old polyester, has good economic worth and the value of environmental protection;
(2) catalyzer that adopts of the preparation method of a kind of low melting point regeneration copolyesters of the present invention, both can the ethylene glycol depolymerization reaction of the PET of catalysis efficiently, also can the copolyreaction again of its depolymerization product of catalysis efficiently.The zinc acetate can avoiding generally adopting at present, zinc-containing metal salt, containing the ionic liquid class catalyst alcoholysis of haloid element to the disadvantageous effect that repolymerization produces; Therefore the preparation method adopting this low melting point to regenerate copolyesters just can be used for copolymerization again without the need to being removed from depolymerization product by catalyzer, greatly can save depolymerization product separating-purifying cost, ensure that repolymerization process carry out smoothly and low melting point regeneration copolyesters quality, for PET serialization functionalization chemistry provides possibility, there is good application prospect;
(2) low melting point provided by the present invention is adopted to regenerate copolyesters preparation method, the catalytic efficiency adopting mass transfer process complicated in solid heterogeneous catalyst alcoholysis and polymerization process to cause can be overcome low, because the binary titanium alkoxide basic metal composite salt catalyzer adopted has good solubility in ethylene glycol;
(3) the binary titanium alkoxide basic metal composite salt catalyzer used in recycled polyester preparation method provided by the present invention containing heavy metal, is not nontoxic or lower toxicity, and therefore prepared low-melting point polyester is safe and reliable.
(4) process for synthetic catalyst used in recycled polyester preparation method provided by the present invention is relatively simple, and reaction conditions is gentle, and reaction process is easy to control, and has good popularizing application prospect.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
First carry out producing of ethylene glycol lithium titanate, it comprises the following steps:
A) by tetraethyl titanate under 50 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetraethyl titanate and ethylene glycol is 1:100;
B) add lithium hydroxide, the mol ratio of lithium hydroxide and tetraethyl titanate is 2.05:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling second alcohol and water reacting and generate, reaction times is 3 hours, after reaction terminates at temperature is 190 DEG C, reaction system pressure is under 0.5atm, the dibasic alcohol evaporation in system is obtained white solid completely in 0.5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol lithium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol lithium titanate is:
Then carry out the preparation method of a kind of low melting point regeneration copolyesters, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol lithium titanate obtained above, the consumption of ethylene glycol lithium titanate is 0.1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste PET polyester bottles fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1500 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 20:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 190 DEG C, and reaction system pressure is 1atm, and the reaction times is 3h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 1.5 times of depolymerization solution quality, at temperature is 150 DEG C, after atmospheric pressure reflux stirs decolouring 5h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 190 DEG C and pressure is 0.5atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, glycol ether three with etc. amount mixing, and the ethylene glycol lithium titanate adding 100ppm is catalyzer, is 150 DEG C in temperature of reaction, pressure is carry out esterification 2h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 9:1 mixing step 4) and step 5) product that obtains, and add 50ppm ethylene glycol lithium titanate as polycondensation catalyst and 50ppm tripotassium phosphate ester heat stabilizer, and at 180 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 220 DEG C, continue reaction 60min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 265 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 100min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 0.903dl/g fusing point: 209.7 DEG C of colours: L:76.43, b:7.14
Embodiment 2
First carry out producing of ethylene glycol sodium titanate, it comprises the following steps:
A) by tetra-n-butyl titanate under 150 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetra-n-butyl titanate and ethylene glycol is 1:50;
B) add sodium hydroxide, the mol ratio of sodium hydroxide and tetra-n-butyl titanate is 2.03:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 210 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling propyl carbinol and water that react and generate, reaction times is 2 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.8atm, the dibasic alcohol evaporation in system is obtained white solid completely in 1min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol sodium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:
Then carry out the preparation method of a kind of low melting point regeneration copolyesters, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate obtained above, the consumption of ethylene glycol sodium titanate is 1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste pure polyester fabric fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1000 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 10:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 180 DEG C, and reaction system pressure is 1atm, and the reaction times is 1h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 220 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid Triethylene Glycol compound: by 1,6-hexanodioic acid, ethylene glycol, Triethylene glycol three with etc. amount mixing, and adding the ethylene glycol metatitanic acid sodium catalyst of 100ppm, is 170 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid Triethylene Glycol compound;
6) in mass ratio for 7:3 mixing step 4) and step 5) product that obtains, 500ppm triphenylphosphate thermo-stabilizer, and at 180 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 240 DEG C, continue reaction 60min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 280 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.15dl/g fusing point: 153.6 DEG C of colours: L:75.43, b:13.56
Embodiment 3
First carry out producing of propylene glycol potassium titanate, it comprises the following steps:
A) by titanium isopropylate under 100 DEG C and nitrogen protection condition, with 1,2-PD Homogeneous phase mixing, the mol ratio of titanium isopropylate and 1,2-PD is 1:80;
B) add potassium hydroxide, the mol ratio of potassium hydroxide and titanium isopropylate is 2.02:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 200 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling isopropyl alcohol and water reacting and generate, reaction times is 4 hours, and after reaction terminates at temperature is 200 DEG C, reaction system pressure is under 0.7atm, in in 1min by the ethylene glycol evaporation in system completely, dibasic alcohol evaporation in system is obtained faint yellow solid completely, utilizes ethanol-Gossypol recrystallized from chloroform to obtain clear crystal three times to this solid, be i.e. obtained propylene glycol potassium titanate;
The structural formula of described alcoholysis catalysts propylene glycol potassium titanate is:
Then carry out the preparation method of a kind of low melting point regeneration copolyesters, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts propylene glycol potassium titanate obtained above, the consumption of propylene glycol potassium titanate is 0.5% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with containing the polyester cotton fragment washing 65% and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 600 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 50:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 160 DEG C, and reaction system pressure is 1atm, and the reaction times is 8h
3) in step 2) add containing quality of activated carbon mark in gained solution be 4% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 4 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 200 DEG C and pressure is 0.6atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) sebacic acid tetraethylene-glycol carboxylate preparation: by 1,10-sebacic acid, ethylene glycol, tetraethylene-glycol three with etc. amount mixing, and the propylene glycol potassium titanate adding 100ppm is catalyzer, is 150 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition sebacic acid tetraethylene-glycol carboxylate;
6) in mass ratio for 6:4 mixing step 4) and step 5) product that obtains, and add 200ppm propylene glycol potassium titanate as polycondensation catalyst and 500ppm tetra-sodium thermo-stabilizer, and at 200 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 220 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 285 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.29dl/g fusing point: 110.7 DEG C of colours: L:70.82, b:13.92
Embodiment 4
First carry out producing of butyleneglycol metatitanic acid rubidium, it comprises the following steps:
A) by metatitanic acid tetra-tert ester under 50 DEG C and nitrogen protection condition, with 1,3 butylene glycol Homogeneous phase mixing, metatitanic acid tetra-tert ester and 1,3 butyleneglycol mol ratios are 1:20;
B) add rubidium hydroxide, the mol ratio 2.01:1 of rubidium hydroxide and metatitanic acid tetra-tert ester, continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 250 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling trimethyl carbinol and water that react and generate, and the reaction times is 5 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.8atm, in in 5min by the 1,3 butylene glycol evaporation in system completely, the dibasic alcohol evaporation in system is obtained yellow solid completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain light yellow crystal three times to this solid, i.e. obtained butyleneglycol metatitanic acid rubidium;
The structural formula of described alcoholysis catalysts butyleneglycol metatitanic acid rubidium is:
Then carry out the preparation method of a kind of low melting point regeneration copolyesters, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts butyleneglycol metatitanic acid rubidium obtained above, the consumption of butyleneglycol metatitanic acid rubidium is 1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with PET polyester film and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 50 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 240 DEG C, and reaction system pressure is 2.5atm, and the reaction times is 30min;
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.9% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 0.5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, glycol ether three with etc. amount mixing, and the butyleneglycol metatitanic acid rubidium adding 50ppm is catalyzer, is 160 DEG C in temperature of reaction, pressure is carry out esterification 2h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 1:2 mixing step 4) and step 5) product that obtains, and add 300ppm diphenyl phosphite thermo-stabilizer, and at 190 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 230 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.87dl/g fusing point: 110.2 DEG C of colours: L:68.7, b:15.9
Embodiment 5
First carry out producing of ethylene glycol sodium titanate, it comprises the following steps:
A) by tetra-n-butyl titanate under 150 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetra-n-butyl titanate and ethylene glycol is 1:60;
B) add sodium hydroxide, the mol ratio of sodium hydroxide and tetra-n-butyl titanate is 2.03:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 210 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling propyl carbinol and water that react and generate, reaction times is 2 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.6atm, the dibasic alcohol evaporation in system is obtained white solid completely in 2min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol sodium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:
Then carry out the preparation method of a kind of low melting point regeneration copolyesters, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate obtained above, the consumption of ethylene glycol sodium titanate is 0.8% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste polyester bottle chip and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 50 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 230 DEG C, and reaction system pressure is 2.5atm, and the reaction times is 30min;
3) in step 2) add containing quality of activated carbon mark in gained solution be 3% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 3 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of sebacic acid glycol ether carboxylate: by 1,10-sebacic acid, ethylene glycol, glycol ether three with etc. amount mixing, and adding the ethylene glycol metatitanic acid sodium catalyst of 100ppm, is 170 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition sebacic acid glycol ether carboxylate;
6) in mass ratio for 8:2 mixing step 4) and step 5) product that obtains, 500ppm ammonium phosphate thermo-stabilizer, and at 220 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 240 DEG C, continue reaction 80min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 285 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.79dl/g fusing point: 137.2 DEG C of colours: L:79.27, b:10.81
Embodiment 6
First carry out producing of ethylene glycol potassium titanate, it comprises the following steps:
A) by titanium isopropylate under 120 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of titanium isopropylate and ethylene glycol is 1:60;
B) add potassium hydroxide, the mol ratio of potassium hydroxide and titanium isopropylate is 2.02:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 220 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling isopropyl alcohol and water reacting and generate, reaction times is 2 hours, after reaction terminates at temperature is 205 DEG C, reaction system pressure is under 0.6atm, the dibasic alcohol evaporation in system is obtained white solid completely in 0.5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol potassium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol potassium titanate is:
Then carry out the preparation method of a kind of low melting point regeneration copolyesters, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol potassium titanate obtained above, the consumption of ethylene glycol potassium titanate is 0.3% of quality of glycol, forms depolymerization solution;
2) depolymerization solution is mixed and the depolymerization reaction carried out under protection of inert gas with knitting containing the polyester cotton blending washing 85%, stir simultaneously, stir speed (S.S.) is 200 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 50:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 200 DEG C, and reaction system pressure is 1.5atm, and the reaction times is 1h;
3) in step 2) add containing quality of activated carbon mark in gained solution be 5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 3 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid Triethylene Glycol compound: by 1; 6-hexanodioic acid; ethylene glycol; Triethylene glycol three with etc. amount mixing, and adding the ethylene glycol potassium titanate catalyst of 100ppm, is 160 DEG C in temperature of reaction; pressure is carry out esterification 3h under 1atm; distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid Triethylene Glycol compound.
6) in mass ratio for 7:3 mixing step 4) and step 5) product that obtains, 50ppm ethylene glycol potassium titanate as polycondensation catalyst, 500ppm primary ammonium phosphate as thermo-stabilizer, and at 220 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 240 DEG C, continue reaction 60min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 275 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 150min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.71dl/g fusing point: 143.5 DEG C of colours: L:73.86, b:12.38
Embodiment 7
First carry out producing of ethylene glycol lithium titanate, it comprises the following steps:
A) by tetraethyl titanate under 60 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetraethyl titanate and ethylene glycol is 1:80;
B) add lithium hydroxide, the mol ratio of lithium hydroxide and tetraethyl titanate is 2.05:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling second alcohol and water reacting and generate, reaction times is 3 hours, after reaction terminates at temperature is 190 DEG C, reaction system pressure is under 0.5atm, the dibasic alcohol evaporation in system is obtained white solid completely in 0.5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol lithium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol lithium titanate is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol lithium titanate obtained above, the consumption of ethylene glycol lithium titanate is 1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste PET polyester bottles fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1500 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 20:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 190 DEG C, and reaction system pressure is 1atm, and the reaction times is 3h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 1.5 times of depolymerization solution quality, at temperature is 150 DEG C, after atmospheric pressure reflux stirs decolouring 5h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 190 DEG C and pressure is 0.5atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, glycol ether three with etc. amount mixing, and the ethylene glycol lithium titanate adding 100ppm is catalyzer, is 165 DEG C in temperature of reaction, pressure is carry out esterification 2h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 9:1 mixing step 4) and step 5) product that obtains, and add 50ppm dimethyl phosphate, 50ppm diphenyl phosphate as thermo-stabilizer, and at 180 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 220 DEG C, continue reaction 60min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 265 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 100min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 0.903dl/g fusing point: 209.7 DEG C of colours: L:76.43, b:7.14
Embodiment 8
First carry out producing of ethylene glycol sodium titanate, it comprises the following steps:
A) by tetra-n-butyl titanate under 120 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetra-n-butyl titanate and ethylene glycol is 1:60;
B) add sodium hydroxide, the mol ratio of sodium hydroxide and tetra-n-butyl titanate is 2.03:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 210 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling propyl carbinol and water that react and generate, reaction times is 2 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.8atm, the dibasic alcohol evaporation in system is obtained white solid completely in 5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol sodium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate obtained above, the consumption of ethylene glycol sodium titanate is 0.1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste pure polyester fabric fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1000 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 10:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 180 DEG C, and reaction system pressure is 1atm, and the reaction times is 1h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 220 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid Triethylene Glycol compound: by 1,6-hexanodioic acid, ethylene glycol, Triethylene glycol three with etc. amount mixing, and adding the ethylene glycol metatitanic acid sodium catalyst of 100ppm, is 170 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid Triethylene Glycol compound;
6) in mass ratio for 7:3 mixing step 4) and step 5) product that obtains, add 100ppm tetra-n-butyl titanate as polycondensation catalyst and 100ppm diphenyl phosphate as thermo-stabilizer, and at 180 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 240 DEG C, continue reaction 60min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 280 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.15dl/g fusing point: 153.6 DEG C of colours: L:75.43, b:13.56
Embodiment 9
First carry out producing of propylene glycol potassium titanate, it comprises the following steps:
A) by titanium isopropylate under 100 DEG C and nitrogen protection condition, with 1,2-PD Homogeneous phase mixing, the mol ratio of titanium isopropylate and 1,2-PD is 1:80;
B) add potassium hydroxide, the mol ratio of potassium hydroxide and titanium isopropylate is 2.02:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 200 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling isopropyl alcohol and water reacting and generate, reaction times is 4 hours, and after reaction terminates at temperature is 200 DEG C, reaction system pressure is under 0.7atm, in in 1min by the ethylene glycol evaporation in system completely, dibasic alcohol evaporation in system is obtained faint yellow solid completely, utilizes ethanol-Gossypol recrystallized from chloroform to obtain clear crystal three times to this solid, be i.e. obtained propylene glycol potassium titanate;
The structural formula of described alcoholysis catalysts propylene glycol potassium titanate is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts propylene glycol potassium titanate obtained above, the consumption of propylene glycol potassium titanate is 0.4% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with containing the polyester cotton fragment washing 65% and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 600 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 30:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 160 DEG C, and reaction system pressure is 1atm, and the reaction times is 5h;
3) in step 2) add containing quality of activated carbon mark in gained solution be 4% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 4 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 200 DEG C and pressure is 0.6atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) sebacic acid tetraethylene-glycol carboxylate preparation: by 1,10-sebacic acid, ethylene glycol, tetraethylene-glycol three with etc. amount mixing, and the propylene glycol potassium titanate adding 100ppm is catalyzer, is 150 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition sebacic acid tetraethylene-glycol carboxylate;
6) in mass ratio for 6:4 mixing step 4) and step 5) product that obtains, and add 10ppm germanium dioxide, 50ppm Germanium tetraacetate as polycondensation catalyst and 200ppm ammonium phosphite as thermo-stabilizer, and at 200 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 220 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 285 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.29dl/g fusing point: 110.7 DEG C of colours: L:70.82, b:13.92
Embodiment 10
First carry out producing of butyleneglycol metatitanic acid rubidium, it comprises the following steps:
A) by metatitanic acid tetra-tert ester under 50 DEG C and nitrogen protection condition, with 1,3 butylene glycol Homogeneous phase mixing, metatitanic acid tetra-tert ester and 1,3 butyleneglycol mol ratios are 1:20;
B) add rubidium hydroxide, the mol ratio of rubidium hydroxide and metatitanic acid tetra-tert ester is 2.01:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 250 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling trimethyl carbinol and water that react and generate, and the reaction times is 5 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.5atm, in in 5min by the 1,3 butylene glycol evaporation in system completely, the dibasic alcohol evaporation in system is obtained yellow solid completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain light yellow crystal three times to this solid, i.e. obtained butyleneglycol metatitanic acid rubidium;
The structural formula of described alcoholysis catalysts butyleneglycol metatitanic acid rubidium is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts butyleneglycol metatitanic acid rubidium obtained above, the consumption of butyleneglycol metatitanic acid rubidium is 0.2% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with PET polyester film and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 600 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 16:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 240 DEG C, and reaction system pressure is 2atm, and the reaction times is 30min;
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.9% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 0.5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, glycol ether three with etc. amount mixing, and the butyleneglycol metatitanic acid rubidium adding 50ppm is catalyzer, is 160 DEG C in temperature of reaction, pressure is carry out esterification 2h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 1:2 mixing step 4) and step 5) product that obtains, and add 10ppm titanium ethylene glycolate, 50ppm titanium isopropylate, 10ppm antimonous oxide, 10ppm antimony glycol, 10ppm antimony acetate as polycondensation catalyst and 50ppm ammonium phosphite, 70ppm phosphoric acid, 80ppm phosphorous acid, 90ppm ortho phosphorous acid, 100ppm tetra-sodium, 20ppm triphenyl phosphite as thermo-stabilizer, and at 190 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 230 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain low melting point regeneration copolyesters.
The main performance index of gained low melting point regeneration copolyester section obtains as follows according to GB/T14190-2008 testing standard:
Limiting viscosity: 1.87dl/g fusing point: 110.2 DEG C of colours: L:68.7, b:15.9
Claims (9)
1. a preparation method for low melting point regeneration copolyesters, is characterized in that comprising the following steps:
1) ethylene glycol depolymerization is carried out to PET polyester:
1.1) alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is dissolved in depolymerizing agent ethylene glycol, forms depolymerization solution;
1.2) depolymerization solution is mixed with PET polyester and stirred carry out depolymerization reaction, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4-50:1, and depolymerization reaction temperature is 160-240 DEG C, and reaction system pressure is 1-2.5atm, and the reaction times is 30min-8h;
The structural formula of described alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is:
Wherein, M
+being IA race metallic cation, is Li
+, Na
+, K
+or Rb
+;
R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4;
2) to decolouring and the purification of depolymerization product, step is as follows:
2.1) in step 1) to add containing quality of activated carbon mark in gained solution be the ethylene glycol dispersion liquid of 0.5-5%, at temperature is 150-220 DEG C, atmospheric pressure reflux stirs decolouring 1-5h;
2.2) gac of impurity and decolouring is then removed after filtration;
2.3) repeating step 2.1) and 2.2) 2-5 time, also namely decolouring and filtration procedure carry out 2-5 time repeatedly, obtain the ethylene glycol solution of the depolymerizing substance after removal of impurities decolouring;
2.4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring under temperature is 190-210 DEG C and pressure is 0.5-0.8atm condition;
3) copolymerization of depolymerization product, concrete step is as follows:
3.1) preparation of modification by copolymerization carboxylate: by binary of fatty acids, ethylene glycol, small molecules polyethers three with etc. amount mixing, and to add a certain amount of titanium ethylene glycolate alkali metal complex be catalyzer, be 150-170 DEG C in temperature of reaction, pressure is stir under 1atm to carry out esterification 2-3h, distillates the water generated in reaction process in time simultaneously, protect with rare gas element in reaction process, reaction terminates rear acquisition aliphatic dibasic acid small molecules polyether ester compound;
3.2) by step 3.1) and step 2) the aliphatic dibasic acid small molecules polyether ester compound that obtains and purification and the depolymerization product after decolouring, polycondensation catalyst and thermo-stabilizer, be 1atm at 180-220 DEG C and pressure, under protection of inert gas, be uniformly mixed by certain mass ratio;
3.3) then, temperature of reaction is increased to 220-240 DEG C, continue reaction 60-120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa;
3.4) then, temperature of reaction is increased to 265-290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 100-180min, namely obtain low melting point regeneration copolyesters;
In described depolymerization solution, the consumption of described binary titanium alkoxide alkali metal coordination compound is the 0.1%-1% of quality of glycol; The molar mass of PET polyester calculates with 192g/mol; The preferred 8-20:1 of mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester, the preferred 180-210 DEG C of depolymerization reaction temperature; Stir during described depolymerization reaction, stir speed (S.S.) is that 50-1500 turns/min; Described depolymerization reaction carries out under protection of inert gas;
The add-on of described polycondensation catalyst is the 0-200ppm of the depolymerization product quality after purifying and decolouring.
2. the preparation method of a kind of low melting point regeneration copolyesters according to claim 1, it is characterized in that, described binary titanium alkoxide alkali metal coordination compound is obtained by following steps:
A) by general formula be Ti (OR)
4titanium compound under 50-150 DEG C and nitrogen protection condition, be dibasic alcohol the HO-R '-OH Homogeneous phase mixing of 2-4 with carbonatoms; Wherein, the saturated hydrocarbon chains structure of R to be carbonatoms be 2-4, R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4;
B) add IA race metal hydroxides MOH, continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180-250 DEG C;
C) in reaction process, backflow dibasic alcohol also gets rid of the lower boiling monohydroxy-alcohol R-OH and water that react and generate, and the reaction times is 2-5 hour, and reaction terminates rear fast by complete for the dibasic alcohol evaporation in system, obtains white or micro-yellow solid;
D) utilized by above-mentioned solid ethanol-Gossypol recrystallized from chloroform repeatedly to obtain colourless or light yellow crystal and be described binary titanium alkoxide alkali metal coordination compound.
3. the preparation method of a kind of low melting point regeneration copolyesters according to claim 2, is characterized in that, Ti (OR)
4be 1:20-100 with the mol ratio of HO-R '-OH; MOH and Ti (OR)
4mol ratio be 2.01-2.05:1; Step c) in, describedly refer to that, at temperature is 190-210 DEG C, reaction system pressure is under 0.5-0.8atm fast, in 0.5-5min by dibasic alcohol evaporation in system completely.
4. the preparation method of a kind of low melting point regeneration copolyesters according to claim 1, is characterized in that, described PET polyester is for being any type of goods made by polyethylene terephthalate and waste and old product by composition.
5. the preparation method of a kind of low melting point regeneration copolyesters according to claim 1, it is characterized in that, the decolouring of described depolymerization product and the step of purification, step 2.1) in, the add-on of the ethylene glycol solution containing gac is 0.5-5 times of depolymerizing substance ethylene glycol solution quality.
6. the preparation method of a kind of low melting point regeneration copolyesters according to claim 1, is characterized in that, step 3.1) in, described binary of fatty acids is 1,6-hexanodioic acid, one or more in 1,10-sebacic acid; Described small molecules polyethers for being polymerized to glycol ether, Triethylene glycol, one or more in tetraethylene-glycol.
7. the preparation method of a kind of low melting point regeneration copolyesters according to claim 1, is characterized in that, step 3.1) in, the add-on of described titanium ethylene glycolate alkali metal complex is 50-100ppm, and stir speed (S.S.) is 50-100rpm; Step 3.2) in, described certain mass of pressing is than mixing, and namely the mass ratio of depolymerization product and aliphatic dibasic acid small molecules polyether ester compound is 9:1-1:2.
8. the preparation method of a kind of low melting point regeneration copolyesters according to claim 1, it is characterized in that, step 3.2) in, described polycondensation catalyst is one or more in binary titanium alkoxide alkali metal coordination compound catalyzer, antimony glycol, antimony acetate, antimonous oxide, Germanium tetraacetate, germanium dioxide, titanium isopropylate, tetrabutyl titanate, titanium ethylene glycolate; Described thermo-stabilizer is one or more in trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, primary ammonium phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate etc.; The add-on of described thermo-stabilizer is the 50ppm-500ppm of the depolymerization product quality after purifying and decolouring.
9. the preparation method of a kind of low melting point regeneration copolyesters according to claim 1, is characterized in that, step 3.2) in, be uniformly mixed and refer to that mixing speed is that 50-80 turns/min, be uniformly mixed 30-60min; Step 3.3) in, at the uniform velocity reduction pressure is 0.5kPa-10kPa/min to the air pressure changing down of 1kPa, and need during reaction to stir, mixing speed is that 50-80 turns/min; Step 3.4) in, continuing at the uniform velocity to reduce pressure to the air pressure changing down of 20Pa is 100Pa-1kPa/min, and continues when reacting to stir, and mixing speed is that 80-120 turns/min.
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| CN107652423B (en) * | 2017-09-18 | 2019-10-11 | 浙江理工大学 | A kind of method of Waste Polyester alcoholysis method preparation regeneration low-melting point polyester |
| CN117448984B (en) * | 2023-11-21 | 2024-04-19 | 南京禾素时代抗菌材料科技集团有限公司 | PHBV composite fiber based on modified low-melting-point PET |
| CN118007260B (en) * | 2024-04-10 | 2024-07-02 | 安徽保尔盈新材料科技有限公司 | Method for producing composite low-melting-point polyester filaments by using regenerated polyester bottle flakes |
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