CN103224620B - Polyester catalyst and preparation method thereof - Google Patents
Polyester catalyst and preparation method thereof Download PDFInfo
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- CN103224620B CN103224620B CN201310139085.7A CN201310139085A CN103224620B CN 103224620 B CN103224620 B CN 103224620B CN 201310139085 A CN201310139085 A CN 201310139085A CN 103224620 B CN103224620 B CN 103224620B
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Abstract
The invention relates to a polyester catalyst and a preparation method thereof. Firstly, attapulgite clay and metatitanic acid are added in an acid solution to prepare a colloidal mixed solution; then a silicate water solution and an aluminium salt solution are added in the colloidal mixed solution; and an attapulgite clay-based titanium polyester catalyst is obtained by fully stirring, filtering, washing, drying and crushing. The catalyst is simple in preparation method and can not cause environment pollution. In a polyester reaction system, activity of the catalyst is increased and color of a product can be improved.
Description
Technical field
The invention belongs to polyester catalyst preparation field, particularly a kind of Inorganic nonmetal mineral functionalization compound and nanocatalyst and preparation method thereof.
Background technology
Polyester is the general name of the polymkeric substance obtained by polyvalent alcohol and polyprotonic acid polycondensation.The thermoplastic resins such as main finger polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyarylester are the important synthetic fiber material of a class and thermoplastic engineering plastic.Wherein PET its there is excellent thermotolerance, insulativity, rebound resilience and wear-resisting, shock-resistance and be widely used in the fields such as fiber, film, wrapping material, electronic apparatus, health care, engineering plastics.At present, the antimony-based catalyst that the catalyzer of the PET production employing in the whole world 90% is is main component with antimonous oxide, antimony acetate and antimony glycol, China is all almost antimony-based catalyst.Because antimony is heavy metal element, in the production of polyester, processing, use and removal process, all adverse influence can be caused to human and environment.In recent years, the environmental consciousness of people is more and more stronger, also more and more higher to the requirement of green consumption, thus also will be more and more stricter to the restriction of antimony.Efficient, environmentally friendly catalyst replaced antimony-based catalyst is used to be the inexorable trend that polyester industrial develops.
The organometallic complex of germanium series catalysts mainly germanium dioxide and germanium, its effect is gentleer, reaction process side reaction is less, stable performance in production process, but its catalytic activity is lower than antimony system, gained polyester ehter bond is more, due to its resource scarcity, expensive, constrain the widespread use of germanium series catalysts.
Titanium series catalyst is just paid close attention to widely and is studied from eighties of last century seventies.In the past few decades, class Titanium series catalyst is successively had to come out.First kind Titanium series catalyst is titanate ester and metatitanic acid saline catalyst mainly, and this kind of catalyst component is single, is very easily hydrolyzed, and catalytic effect is unstable, the serious yellowing of product colour.Equations of The Second Kind Titanium series catalyst is the catalyzer of titanyl compound class, usually other elements are mixed and titanium forms composite oxides in the component of this kind of catalyzer, such as amorphous ti silica or titanium Zirconium oxide etc., these elements be incorporated in the catalytic selectivity improving Titanium series catalyst to a certain extent.But this titanium oxide nanoparticle is easily reunited, and is difficult to be uniformly dispersed at polyester catalyst system, adds the complicacy of mass transfer, and then reduces speed of response, add side reaction, cause the easy yellowing of the color of product.In addition, there is the problem of particle agglomeration in oxide-based catalyzer in use, causes the specific surface area of catalyzer to reduce, and usage quantity increases, and its use cost also increases thereupon.The complex compound class catalyzer of third generation Titanium series catalyst titanium, the moiety more complicated of this kind of catalyzer, and owing to introducing baroque part in most titanium complex catalyzer, can not dissolve each other with ethylene glycol, heterogeneous property in system is comparatively strong, and therefore current result of use is still not ideal enough.In addition, the noxious solvent such as benzene, toluene can be introduced in the preparation process of preparation technology's more complicated of this kind of catalyzer, and the comparison of ingredients used in raw material is many, particularly such catalyzer a lot, make the inadequate environmental protection of preparation process.Due to its production technique more complicated, so the production cost of this kind of catalyzer is higher, also larger on the impact of production of polyester cost.
Summary of the invention
For the problem existing for above-mentioned background technology, the invention provides the new polyester catalyzer of a kind of easy dispersion, high reactivity, safety non-toxic.
The invention provides a kind of polyester catalyst, is be carried on by titanium dioxide, silicon-dioxide and aluminium sesquioxide the composite catalyst formed in recessed soil.
The present invention is by titanium oxide load on recessed soil surface, and so can introduce Si oxide and aluminum oxide, form recessed soil-Ti-Si-Al quaternary composite catalyst, concrete preparation method is:
(1) to hydrogen ion content be 0.2 ~ 1mol/L acid solution in add recessed soil and metatitanic acid, at 10 ~ 40 DEG C react 24 ~ 96 hours, obtain gluey mixed solution,
Wherein, acid solution is selected from hydrochloric acid or nitric acid, and the mass ratio of metatitanic acid and recessed soil is 0.37 ~ 1.84:1,
The quality summation of metatitanic acid and recessed soil, with the mass ratio of acid solution, namely m (metatitanic acid+recessed soil): m (acid solution)=0.05 ~ 0.25:1;
(2) step (1) gained colloid mixed solution is warming up to 70 ~ 95 DEG C, aqueous silicate solution is added while stirring in colloid mixed solution, when the pH value of system reaches 9 ~ 10, stop adding aqueous silicate solution, insulated and stirred 0.5 ~ 3 hour, adding aluminum salt solution to the pH value of system is 5 ~ 7, insulated and stirred 0.5 ~ 1 hour, filtration, washing, drying, pulverizing obtain recessed soil matrix titanium series polyester catalyst
Wherein, aqueous silicate solution is selected from sodium silicate solution or potassium silicate solution, and its Solute mass percentage composition is 5 ~ 25%,
Aluminum salt solution is selected from Tai-Ace S 150, aluminum nitrate or aluminum chloride, and concentration is 0.1 ~ 0.5mol/L,
By adding silicate and aluminium salt, introducing Si oxide and aluminum oxide, having Accommodation to the activity of catalyzer, improve the form and aspect of product.
The invention has the beneficial effects as follows:
1, utilize silicate and aluminium salt hydrolysis generation Si oxide and aluminum oxide to adjust catalyst activity, improve catalyzer in the dispersiveness of pet reaction system, improve the form and aspect of product.
2, recessed soil matrix titanium series polyester catalyst has the filamentary structure of recessed soil, makes it in reaction system, form mutual support structure, can not precipitate because of reunion, solves titanium oxide catalyst difficulty dispersion in polyester synthesis and the problem of easily reuniting well.
3, recessed soil matrix titanium series polyester catalyst not only plays the effect of catalyzer in polyester synthesis, but also can play the effect of nucleator, can be used for improving polyester crystalline-granular texture, improves crystallization rate, strengthens mechanical property, shorten shaping cycle.
4, preparation method is simple, can not cause environmental pollution.
Embodiment
Embodiment 1:
1, be in the hydrochloric acid soln of 0.2 mol/L to 74.0 kg of hydrogen ion contents, add 1.0 kilograms of metatitanic acids and 2.7 kilograms of recessed soil respectively, react 24 hours under 40 DEG C of conditions, obtain gluey mixed solution;
2, the colloid mixed solution of step 1 gained is warming up to 70 DEG C, add in colloid mixed solution while stirring mass percentage be 25% sodium silicate aqueous solution to the pH value of system be 9, stop adding sodium silicate aqueous solution, insulated and stirred 3 hours, the liquor alumini chloridi adding 0.1 mol/L is 7 to the pH value of system, insulated and stirred 0.5 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti-Si-Al quaternary composite catalyst.
Embodiment 2:
1, be in the salpeter solution of 1 mol/L to 12.36 kg of hydrogen ion contents, add 2.0 kilograms of metatitanic acids and 1.09 kilograms of recessed soil respectively, react 96 hours under 10 DEG C of conditions, obtain colloid mixed solution;
2, the colloid mixed solution of step 1 gained is warming up to 95 DEG C, add in colloid mixed solution while stirring mass percentage be 10% potassium silicate aqueous solution to the pH value of system be 10, stop adding potassium silicate aqueous solution, insulated and stirred 0.5 hour, the aluminum nitrate solution adding 0.5 mol/L is 5 to the pH value of system, insulated and stirred 1 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti-Si-Al quaternary composite catalyst.
Embodiment 3:
1, be in the hydrochloric acid soln of 0.6 mol/L, add 1.5 kilograms of metatitanic acids and 1.36 kilograms of recessed soil respectively to 19.1 kg of hydrogen ion contents, react 60 hours under 25 DEG C of conditions, obtain colloid mixed solution.
2, the colloid mixed solution of step 1 gained is warming up to 82 DEG C, add in colloid mixed solution while stirring mass percentage be 20% sodium silicate aqueous solution to the pH value of system be 9.5, stop adding sodium silicate aqueous solution, insulated and stirred 2 hours, the alum liquor adding 0.3 mol/L is 6 to the pH value of system, insulated and stirred 0.8 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti-Si-Al quaternary composite catalyst.
Embodiment 4:
1, be in the salpeter solution of 0.5 mol/L, add 1.5 kilograms of metatitanic acids and 1.0 kilograms of recessed soil respectively to 25.0 kg of hydrogen ion contents, react 45 hours under 30 DEG C of conditions, obtain colloid mixed solution.
2, the colloid mixed solution of step 1 gained is warming up to 90 DEG C, add in colloid mixed solution while stirring mass percentage be 15% potassium silicate aqueous solution to the pH value of system be 10, stop adding potassium silicate aqueous solution, insulated and stirred 1 hour, the aluminum nitrate solution adding 0.2 mol/L is 6.5 to the pH value of system, insulated and stirred 0.7 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti-Si-Al quaternary composite catalyst.
Embodiment 5:
1, be in the hydrochloric acid soln of 0.8 mol/L, add 1.4 kilograms of metatitanic acids and 2.0 kilograms of recessed soil respectively to 17.0 kg of hydrogen ion contents, react 72 hours under 15 DEG C of conditions, obtain colloid mixed solution.
2, the colloid mixed solution of step 1 gained is warming up to 75 DEG C, add in colloid mixed solution while stirring mass percentage be 5% sodium silicate aqueous solution to the pH value of system be 9, stop adding sodium silicate aqueous solution, insulated and stirred 2.5 hours, the liquor alumini chloridi adding 0.4 mol/L is 5.5 to the pH value of system, insulated and stirred 0.6 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti-Si-Al quaternary composite catalyst.
Comparative example 1:
1, be in the hydrochloric acid soln of 0.2 mol/L, add 1.0 kilograms of metatitanic acids and 2.7 kilograms of recessed soil respectively to 74.0 kg of hydrogen ion contents, react 24 hours under 40 DEG C of conditions, obtain colloid mixed solution;
2, the colloid mixed solution of step 1 gained is warming up to 70 DEG C, add in colloid mixed solution while stirring mass percentage be 25% aqueous sodium hydroxide solution to the pH value of system be 9, stop adding aqueous sodium hydroxide solution, insulated and stirred 3 hours, the hydrochloric acid soln adding 0.1 mol/L is 7 to the pH value of system, insulated and stirred 0.5 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti binary composite catalyst.
Comparative example 2:
1, be in the hydrochloric acid soln of 0.2 mol/L, add 1.0 kilograms of metatitanic acids and 2.7 kilograms of recessed soil respectively to 74.0 kg of hydrogen ion contents, react 24 hours under 40 DEG C of conditions, obtain colloid mixed solution;
2, the colloid mixed solution of step 1 gained is warming up to 70 DEG C, add in colloid mixed solution while stirring mass percentage be 25% sodium silicate aqueous solution to the pH value of system be 9, stop adding sodium silicate aqueous solution, insulated and stirred 3 hours, the hydrochloric acid soln adding 0.1 mol/L is 7 to the pH value of system, insulated and stirred 0.5 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti-Si ternary complex catalyst.
Comparative example 3:
1, be in the hydrochloric acid soln of 0.2 mol/L, add 1.0 kilograms of metatitanic acids and 2.7 kilograms of recessed soil respectively to 74.0 kg of hydrogen ion contents, react 24 hours under 40 DEG C of conditions, obtain colloid mixed solution;
2, the colloid mixed solution of step 1 gained is warming up to 70 DEG C, add in colloid mixed solution while stirring mass percentage be 25% aqueous sodium hydroxide solution to the pH value of system be 9, stop adding aqueous sodium hydroxide solution, insulated and stirred 3 hours, the liquor alumini chloridi adding 0.1 mol/L is 7 to the pH value of system, insulated and stirred 0.5 hour, filtration, washing, drying, pulverizing obtain recessed soil-Ti-Al ternary complex catalyst.
The evaluation of polyester catalyst catalytic performance:
The quality of polyester polycondensation catalyst is mainly evaluated from two aspects: one is catalytic activity, and two is form and aspect of product.The method of the reactive behavior of usual research polycondensation catalyst has 3 kinds: when other reaction conditionss are identical, compare the molecular weight of same time gained PET, generally represent with inherent viscosity; (2) when other reaction conditionss are identical, the polycondensation time required when reaching same molecular amount is compared; (3) condensation polymerization speed constant is measured.Method (1), (2) are simple, and method (3) is more complicated.Adopt (2) method in this experiment, the length namely by comparing the polycondensation time characterizes the speed of polycondensation, namely the size of catalytic activity.The form and aspect of polyester product, measure with colour-difference meter, evaluate according to L and b in international standard color system CIE-L, a, b, wherein L value is whiteness, and b value is yellowness index.
Specific experiment method is:
The mixture of terephthalic acid (PTA), ethylene glycol (EG) (PTA:EG=1.4) and catalyzer (above embodiment and comparative example in prepared) is put into reactor, and (catalyst levels is in the mass ratio with PTA, account for the 180 μ gg-1 of PTA), esterification is carried out under 260 DEG C and 400 ~ 430kPa, when esterification yield reaches more than 95%, start to vacuumize, temperature is risen to 280 DEG C simultaneously.When in still, vacuum overbottom pressure is about 70Pa, start as polycondensation, writing time.Along with the carrying out of polycondensation, answer the continuous increase of system viscosity, agitator power constantly raises, when agitator power rises to prescribed value (now the limiting viscosity of polycondensation product reaches about 0.66dL/g), polycondensation terminates, and stops heating, discharging granulation, the polycondensation time is shorter, and catalyst activity is higher.
The evaluation result of embodiment and comparative example gained polyester catalyst catalytic performance is as shown in table 1.
As seen from Table 1, gained of the present invention recessed soil matrix Titanium series catalyst has higher catalytic activity, and the polyester product catalyzed and synthesized also has good form and aspect.
Table 1 embodiment and comparative example gained polyester catalyst are on the impact of polycondensation reaction time and quality product
Claims (6)
1. a preparation method for polyester catalyst, is characterized in that:
Described polyester catalyst is carried on by titanium dioxide, silicon-dioxide and aluminium sesquioxide the composite catalyst formed in recessed soil,
The concrete steps of described preparation method are:
(1) to hydrogen ion content be 0.2 ~ 1mol/L acid solution in add recessed soil and metatitanic acid, at 10 ~ 40 DEG C react 24 ~ 96 hours, obtain gluey mixed solution;
(2) step (1) gained colloid mixed solution is warming up to 70 ~ 95 DEG C, aqueous silicate solution is added while stirring in colloid mixed solution, when the pH value of system reaches 9 ~ 10, stop adding aqueous silicate solution, insulated and stirred 0.5 ~ 3 hour, adding aluminum salt solution to the pH value of system is 5 ~ 7, insulated and stirred 0.5 ~ 1 hour, filter, washing, dry, pulverize and obtain recessed soil matrix titanium series polyester catalyst.
2. the preparation method of polyester catalyst as claimed in claim 1, is characterized in that: the acid solution described in step (1) is selected from hydrochloric acid soln or salpeter solution.
3. the preparation method of polyester catalyst as claimed in claim 1, is characterized in that: the mass ratio of the metatitanic acid described in step (1) and recessed soil is 0.37 ~ 1.84:1.
4. the preparation method of polyester catalyst as claimed in claim 1, it is characterized in that: the quality summation of the metatitanic acid described in step (1) and recessed soil, is 0.05 ~ 0.25:1 with the mass ratio of acid solution.
5. the preparation method of polyester catalyst as claimed in claim 1, it is characterized in that: the aqueous silicate solution described in step (2) is selected from sodium silicate solution or potassium silicate solution, its Solute mass percentage composition is 5 ~ 25%.
6. the preparation method of polyester catalyst as claimed in claim 1, it is characterized in that: the aluminum salt solution described in step (2) is selected from alum liquor, aluminum nitrate solution or liquor alumini chloridi, concentration is 0.1 ~ 0.5mol/L.
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| CN101565500A (en) * | 2008-04-23 | 2009-10-28 | 中国科学院化学研究所 | Polyester/clay nanometer composite material, special catalyst thereof and methods for preparing polyester/clay nanometer composite material and special catalyst thereof |
| CN101787224A (en) * | 2010-01-19 | 2010-07-28 | 江苏工业学院 | Compound of high-whiteness clay and preparation method thereof |
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| CN101565500A (en) * | 2008-04-23 | 2009-10-28 | 中国科学院化学研究所 | Polyester/clay nanometer composite material, special catalyst thereof and methods for preparing polyester/clay nanometer composite material and special catalyst thereof |
| CN101787224A (en) * | 2010-01-19 | 2010-07-28 | 江苏工业学院 | Compound of high-whiteness clay and preparation method thereof |
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