CN105694009A - Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol - Google Patents
Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol Download PDFInfo
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- CN105694009A CN105694009A CN201410685730.XA CN201410685730A CN105694009A CN 105694009 A CN105694009 A CN 105694009A CN 201410685730 A CN201410685730 A CN 201410685730A CN 105694009 A CN105694009 A CN 105694009A
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- cerium
- zirconium
- montmorillonite
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Abstract
The invention relates to a zirconium/cerium-montmorillonite composite catalyst. The catalyst is characterized by being prepared by subjecting a hydroxide fluid suspension of zirconium/cerium and a montmorillonite fluid suspension with a granularity of less than 2 [mu]m to a hybrid reaction and then carrying out washing, drying and roasting, wherein the percentage content of Zr is 1 to 12%, and the percentage content of Ce is 1 to 17%. The invention also relates to a method for preparing polyester glycol by using the above-mentioned novel catalyst to replace a conventional metal organic catalyst. Polyester glycol prepared by using the method has an acid value of lower than 0.1 mg KOH/g and extremely low catalyst residual; and prepared elastomer has excellent hydrolysis resistance.
Description
Technical field
The present invention relates to the heterogeneous catalyst of a kind of polyester produced by being supported on by zirconium/cerium compound in montmorillonite；The method that the invention also relates to prepare polyester diol with Above-mentioned catalytic agent。
Background technology
Polyester is important industrial copolymer, for the polyol component in polyurethane system。Polyester is prepared by low-molecular-weight polycarboxylic acid (such as adipic acid) with the esterification of low molecular weight polyols (such as diethylene glycol), condensation and is obtained。Catalyst is generally used in above-mentioned reaction to shorten reactor holding time and to form high molecular。
A lot of commercial runs use such as the metallorganic such as titanium, stannum or antimony as the catalyst of esterification, ester exchange or polycondensation reaction, but above-mentioned metallorganic catalyst remain in the polyester, have undesirable effect in further polyurethane production。Therefore about the 10ppm of the weight content making consumption be production of polyester thing of above-mentioned catalyst is reduced, even so low content easily produces gelatin phenomenon when also resulting in polyester with Isocyanate prepolymers, in addition the acid number of polyester is also high especially, for about 1mgKOH/g, if being reduced to desirable acid number (below 0.1mgKOH/g), then need longer polycondensation reaction time, so may result in polyester easily oxidized and cause the risk of xanthochromia, the polyurethane elastomer of subsequent production is caused the quality impact can not ignore。
In order to polyester disclosure satisfy that subsequent production needs, in polyester, generally add the gel inhibitor of about the 10ppm being about its weight content, such as phosphoric acid, sulphuric acid or chlorinated amide etc., the anti-hydrolytic performance degradation of its synthesized polyurethane elastomer can be caused so again。
Summary of the invention
For the above-mentioned deficiency of prior art, according to embodiments of the invention, it is desirable to provide a kind of new catalyst substitutes existing metallorganic catalyst, is used for preparing polyester diol。
According to embodiments of the invention, it is further desirable to utilize aforementioned new catalyst to substitute existing metallorganic catalyst preparing polyester diol, and this type of polyester diol is for preparing the polyurethane elastomer of excellent hydrolysis resistance。
According to embodiment, a kind of zirconium/cerium-montmorillonite Composite catalyst provided by the invention, its innovative point is in that, after it is carried out hybrid reaction by the hydroxide suspension liquid of zirconium/cerium and the granularity montmorillonite suspension liquid less than 2 microns, scrubbed, dry and roasting and prepare, wherein: the percentage composition of Zr is 1%～12%, the percentage composition of Ce is 1%～17%。
According to an embodiment, in the aforementioned zirconium/cerium-montmorillonite Composite catalyst of the present invention, PH=7～12 of the hydroxide suspension liquid of described zirconium/cerium, by being the ZrOCl of 0.1mol/L～0.5mol/L by concentration2And CeCl3Aqueous solution adds to stir in the NaOH aqueous solution that concentration is 0.5mol/L～2mol/L and forms；Montmorillonite suspension liquid is to use the granularity montmorillonite less than 2 microns and distilled water mixed preparing to form, and both weight ratios are 1:5～1:20。
According to an embodiment, in the aforementioned zirconium/cerium-montmorillonite Composite catalyst of the present invention, the hydroxide suspension liquid of zirconium/cerium and the mixed proportion of montmorillonite suspension liquid are 0.1:1～1:1, wash to chloride ion lower than 10 after hybrid reaction-4Mol/L, and dry at 100 DEG C～120 DEG C, roasting at 300 DEG C～350 DEG C。
According to embodiment, the preparation method of a kind of polyester diol provided by the invention, its innovative point is in that, mixing dihydroxylic alcohols and dicarboxylic acids heat under nitrogen or inert gas atmosphere to 150～190 DEG C and carry out polycondensation reaction, the mol ratio of the hydroxyl of mixing dihydroxylic alcohols and the carboxyl of dicarboxylic acids is (1～2): 1, when acid number reaches 18～40mgKOH/g, add aforementioned zirconium/cerium-montmorillonite Composite catalyst, reaction system is decompressed to-0.099Mpa～-0.1Mpa, temperature is increased to 220 DEG C～240 DEG C, until acid number reaches below 0.1mgKOH/g stopped reaction, prepare polyester diol。
According to an embodiment, in the preparation method of previous polyesters dihydroxylic alcohols of the present invention, the addition of described zirconium/cerium-montmorillonite Composite catalyst is 0.05%～0.5%。
According to an embodiment, in the preparation method of previous polyesters dihydroxylic alcohols of the present invention, mixing dihydroxylic alcohols is ethylene glycol, propylene glycol, BDO, 2-methyl propanediol, 1,6-hexanediol or diglycol arbitrarily two or more glycol。
According to an embodiment, in the preparation method of previous polyesters dihydroxylic alcohols of the present invention, dicarboxylic acids is adipic acid。
As described above, the present invention relates to a kind of direct esterification mixing dihydroxylic alcohols and adipic acid under the existence that a kind of zirconium/cerium compound is supported on montmorillonite, also described heterogeneous catalysis can be placed in fixed bed reactors。In both embodiments, according to method well known in the art, water is removed by the methods such as distillation or noble gas stripping, vacuum that reduce pressure continuously from reactor。
In other words, the inventive method can carry out according to so-called " intermittent vacuum-fusion method " or " purification-gas-fusion method "。
According to the first situation, device is closed system, consists essentially of: the stirring-type reactor of equipment agitator, distillation column, condenser, receptor, and vacuum pump。Under agitation but under airfree condition, in reactor, heat initial feed。Heat is provided by electric energy, high steam or heat transfer medium。In the first stage of reaction, keep the temperature at the temperature greater than or equal to 150 DEG C under ambient pressure, it is preferable that about 150 DEG C～190 DEG C, by the product water of about 90% is distilled off。
So obtaining the mixture of oligoester, its polycondensation immediately in second stage of reaction becomes polyester。In the first embodiment, catalyst is added in reactor, and in this second embodiment, liquid phase is being circulated by fixed bed reactors。React to about-0.099Mpa condition at about 190 DEG C～225 DEG C and step-by-step decompression。Reaction residual water and the by-product such as Low Molecular Weight Aldehydes and ketone of excessive polyhydric alcohol and a small amount of (relative to final PEPA for ppm amount to exist) are distilled off from mixture。This process is often monitored by measuring acid number, hydroxyl value and viscosity。
According to the second situation (i.e. purification-gas-fusion method), in the second stage of reaction, noble gas (such as, nitrogen) is made to remove retortable product by mixture rather than by reducing pressure。It might be noted that the method can negatively influence the consumption of polyhydric alcohol, therefore device is it is generally required to carry out suitable improvement, for instance load onto gas access to reactor。Make reactant mixture reaction until reaching required conversion and final recovery。
The inventive method represents the new effective ways that preparation has the polyester of excellent hydrolytic resistance and mechanical strength especially。
Embodiment at any time will demonstrate that, the polyester diol prepared by the inventive method shows that acid number is lower than 0.1mgKOH/g, and catalyst residual quantity is extremely low, and obtained elastomer anti-hydrolytic performance is excellent。The product prepared by the inventive method is mainly used as the high-strength damping element bearing dynamic fatigue, such as the bumper and absorbing shock element and Bridge Seismic block etc. of the vehicles such as automobile。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further。These embodiments are interpreted as being merely to illustrate the present invention rather than limiting the scope of the invention。After having read the content that the present invention records, the present invention can be made various changes or modifications by those skilled in the art, and these equivalence changes and modification fall into the scope of the claims in the present invention equally。
Embodiment 1 prepares catalyst of the present invention
Embodiment 1.1
First it is the ZrOCl of 0.1mol/L by molar concentration2And CeCl3Aqueous solution adds in the NaOH aqueous solution of 0.7mol/L, strong agitation, and controls pH value in the scope of 7～12, prepares the hydroxide suspension liquid of zirconium/cerium after placing 48 hours；Secondly using the granularity montmorillonite less than 2 microns and distilled water mixed preparing montmorillonite suspension liquid, both weight is 1:10；Finally by by the hydroxide suspension liquid of zirconium/cerium and montmorillonite suspension liquid hybrid reaction, its mixed proportion is 1:5, washs to chloride ion lower than 10-4Mol/L, dries at 100 DEG C, carries out roasting at 300 DEG C。It is 2.1% that acquisition has Zr content, and Ce content is the zirconium/cerium-montmorillonite Composite catalyst of 3.2% (gross weight relative to catalyst)。
Embodiment 1.2
Use and the similar approach described in example 1 above, be the ZrOCl of 0.1mol/L by molar concentration2CeCl with 0.5mol/L3Aqueous solution adds in the NaOH aqueous solution of 2mol/L, prepares the hydroxide suspension liquid of zirconium/cerium。After the hydroxide suspension liquid of zirconium/cerium and montmorillonite suspension liquid hybrid reaction, dry at 120 DEG C, at 350 DEG C, carry out roasting。It is 2.1% that acquisition has Zr content, and Ce content is the zirconium/cerium-montmorillonite Composite catalyst of 16.2% (gross weight relative to catalyst)。
Embodiment 1.3
Use and the similar approach described in example 1 above, be the ZrOCl of 0.5mol/L by molar concentration2CeCl with 0.1mol/L3Aqueous solution adds in the NaOH aqueous solution of 2mol/L, prepares the hydroxide suspension liquid of zirconium/cerium。After the hydroxide suspension liquid of zirconium/cerium and montmorillonite suspension liquid hybrid reaction, dry at 110 DEG C, at 325 DEG C, carry out roasting。It is 10.5% that acquisition has Zr content, and Ce content is the zirconium/cerium-montmorillonite Composite catalyst of 3.2% (gross weight relative to catalyst)。
Embodiment 1.4
Using and the similar approach described in example 1 above, by by the hydroxide suspension liquid of zirconium/cerium and montmorillonite suspension liquid hybrid reaction, its mixed proportion is 1:10。After the hydroxide suspension liquid of zirconium/cerium and montmorillonite suspension liquid hybrid reaction, dry at 100 DEG C, at 350 DEG C, carry out roasting。It is 1.05% that acquisition has Zr content, and Ce content is the zirconium/cerium-montmorillonite Composite catalyst of 1.6% (gross weight relative to catalyst)。
Embodiment 1.5
Using and the similar approach described in example 1 above, by by the hydroxide suspension liquid of zirconium/cerium and montmorillonite suspension liquid hybrid reaction, its mixed proportion is 1:2。After the hydroxide suspension liquid of zirconium/cerium and montmorillonite suspension liquid hybrid reaction, dry at 120 DEG C, at 300 DEG C, carry out roasting。It is 5.25% that acquisition has Zr content, and Ce content is the zirconium/cerium-montmorillonite Composite catalyst of 8% (gross weight relative to catalyst)。
The synthesis of embodiment 2 polyester diol
Embodiment 2.1～2.9
It is used for preparing polyester diol (embodiment 2.1～2.7) by zirconium/cerium-montmorillonite Composite catalyst that embodiment 1.1～1.5 prepares。By tetraisopropyl titanate (embodiment 2.8) catalyst of making comparisons。Comparative example 2.9 describes and is not added with people's catalyst preparing polyester diol。
By 3.09kg1,4-butanediol, 2.13kg ethylene glycol heat together with 9.03kg adipic acid is under nitrogen or inert gas atmosphere to 150-190 DEG C and carry out dehydrating polycondensation, when acid number reaches 18～40mgKOH/g, add and add the catalyst prepared from embodiment 1.1～1.5, while be decompressed to-0.099Mpa or-0.1Mpa, while raise the temperature to 225 DEG C (220-240 DEG C), until hydroxyl value reaches about 56mgKOH/g, and acid number reaches below 0.1mgKOH/g stopped reaction, prepare polyester diol。The persistent period of vacuum phase is the feature of the catalyst used and is defined as the response time。
Table 1
Table 1: the embodiment of the present invention 2.1～2.7；Comparative example 2.8～2.9
Table 1 illustrates, with tetraisopropyl titanate (embodiment 2.8), zirconium/cerium-montmorillonite Composite the catalyst (in embodiment 2.1～2.7) of the present invention has better catalysis activity, the acid number of gained polyester diol is below 0.1mgKOH/g, and the percentage composition of metal ion is extremely low, do not affect the prepolymerization reaction of polyester and isocyanates。When not using catalyst (embodiment 2.9), as expected, it is necessary to adopt long response time and disadvantageous conversion ratio。
The synthesis of embodiment 3 polyurethane elastomer
Embodiment 3.1～3.10
It is used for preparing polyurethane elastomer (embodiment 3.1～3.9) by the polyester diol that embodiment 2.1～2.9 prepares。The reactor product of embodiment 2.8 adds 20ppm phosphoric acid process, as comparative example 3.10。
Degassed 60min under the polyester diol (100 weight portion) that embodiment 2.1～2.9 the is prepared low pressure at 125 DEG C with lower than-0.099Mpa。Stirring adds NDI (naphthalene-1 of 21 weight portions, 5-diisocyanate), after 2min, progressively applies vacuum, and after 15min, temperature no longer raises and exothermic reaction stopping。Then add dry BDO (4 weight portion) when being formed without bubble through stirring in 30 seconds, subsequently reactant mixture is poured in the mould (about 110 DEG C) of heat。After about 20min, it is removed from the molds foundry goods, then tempering 24 hours at 110 DEG C。
Foundry goods reached its final hardness after about 14 days and shows the performance shown in table 2。
Claims (7)
1. zirconium/cerium-montmorillonite Composite catalyst, it is characterized in that, after it is carried out hybrid reaction by the hydroxide suspension liquid of zirconium/cerium and the granularity montmorillonite suspension liquid less than 2 microns, scrubbed, dry and roasting and prepare, wherein: the percentage composition of Zr is 1%～12%, the percentage composition of Ce is 1%～17%。
2. zirconium/cerium-montmorillonite Composite catalyst according to claim 1, is characterized in that, PH=7～12 of the hydroxide suspension liquid of described zirconium/cerium, by concentration is the ZrOCl of 0.1mol/L～0.5mol/L2And CeCl3Aqueous solution adds to stir in the NaOH aqueous solution that concentration is 0.5mol/L～2mol/L and forms；Montmorillonite suspension liquid is to use the granularity montmorillonite less than 2 microns and distilled water mixed preparing to form, and both weight ratios are 1:5～1:20。
3. zirconium/cerium-montmorillonite Composite catalyst according to claim 2, is characterized in that, the hydroxide suspension liquid of zirconium/cerium and the mixed proportion of montmorillonite suspension liquid are 0.1:1～1:1, wash to chloride ion lower than 10 after hybrid reaction-4Mol/L, and dry at 100 DEG C～120 DEG C, roasting at 300 DEG C～350 DEG C。
4. the preparation method of a polyester diol, it is characterized in that, mixing dihydroxylic alcohols and dicarboxylic acids heat under nitrogen or inert gas atmosphere to 150～190 DEG C and carry out esterification, the mol ratio of the hydroxyl of mixing dihydroxylic alcohols and the carboxyl of dicarboxylic acids is (1～2): 1, when acid number reaches 18～40mgKOH/g, add the zirconium/cerium-montmorillonite Composite catalyst in any of the one of claim 1-3, reaction system is decompressed to-0.099Mpa～-0.1Mpa, temperature is increased to 220 DEG C～240 DEG C, until acid number reaches below 0.1mgKOH/g stopped reaction, prepare polyester diol。
5. the preparation method of polyester diol according to claim 4, is characterized in that, the addition of described zirconium/cerium-montmorillonite Composite catalyst is 0.05%～0.5%。
6. the preparation method of the polyester diol according to claim 4 or 5, is characterized in that, mixing dihydroxylic alcohols is ethylene glycol, propylene glycol, BDO, 2-methyl propanediol, 1,6-hexanediol or diglycol arbitrarily two or more glycol。
7. the preparation method of polyester diol according to claim 6, is characterized in that, dicarboxylic acids is adipic acid。
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Cited By (1)
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| CN108203536A (en) * | 2016-12-20 | 2018-06-26 | 上海凯众材料科技股份有限公司 | Thermoplastic polyester elastomer composition and manufacture the method for secondary spring with it |
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