CN105131269A - Preparation method of environment-friendly titanium-phosphor coordination composite catalyst, and PBS producing method using environment-friendly titanium-phosphor coordination composite catalyst - Google Patents
Preparation method of environment-friendly titanium-phosphor coordination composite catalyst, and PBS producing method using environment-friendly titanium-phosphor coordination composite catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of an environment-friendly titanium-phosphor coordination composite catalyst, and a PBS producing method using the environment-friendly titanium-phosphor coordination composite catalyst, wherein the environmental-friendly titanium-phosphor coordination composite catalyst is high in efficiency and selectivity, and is suitable for PBS production. The preparation method comprises following steps: 1,4-butanediol, an organic phosphorus compound, and a hindered phenol antioxidant are delivered into a reaction vessel at a certain ratio for full stirring and mixing; an organic titanium compound is added slowly, an obtained mixture is heated to 40 to 200 DEG C, and is reacted for 0.5 to 12h so as to obtain the homogeneous-phase liquid-state titanium-phosphor coordination composite catalyst. The environment-friendly titanium-phosphor coordination composite catalyst is applied to PBS production taking butanedioic acid and butanediol as raw materials; melt index of obtained PBS is lower than 3g/10min (190 DEG C, 2.16kg), intrinsic viscosity is as high as 2.05dL/g, number-average molecular weight is 100 thousand or higher, L value >=80, a value>=-0.43, b value<=5.24, and color value is much higher than that required in a national standard.
Description
Technical field
The present invention relates to a kind of preparation method being suitable for the environment-friendly type titanium-phosphorus coordination composite catalyst of efficient, the highly selective that PBS produces, also relate to a kind of PBS production method adopting this composite catalyst, belong to chemical technology field.
Background technology
Poly-is a kind of thermoplastics to succinic acid-butanediol ester (PBS), it is the polymkeric substance of the fully biodegradable of generally acknowledging in the world, compared with polycaprolactone (PCL), poly(lactic acid) (PLA), PBS has higher fusing point, has superior resistance toheat and mechanical property; Compared with the degradable material such as poly 3-hydroxy butyrate (PHB), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), PBS's is cheap, and cost is only the former 1/3 even lower, and performance is excellent in mechanical property, processing characteristics etc.PBS excellent in mechanical performance, close to PP and ABS plastic; Resistance toheat is good, and heat-drawn wire is close to 100 DEG C, and modified use temperature more than 100 DEG C, can overcome the shortcoming low with other biological degradative plastics heat resisting temperature; Processing characteristics is very good, can carry out all kinds of forming process on existing plastic working general-purpose equipment, is that current degradative plastics processing characteristics is best, simultaneously can the weighting material such as blended a large amount of calcium carbonate, starch, obtains economic goods.All development biodegradable plastic industry is classified as important industry content in " national medium & long term sci-tech development program outline " and Eleventh Five-Year Plan science and technology development planning." industry restructuring guidance list (basis in 2011) " that the National Development and Reform Commission issues encourages series products catalogue all to comprise " biodegradable plastic and series product development, production and application " (light industry), the exploitation of the new polyester such as poly-succinic fourth diester (PBS) and the fiber ", produce and apply " (weaving).PBS has been shortlisted for and has become the full-biodegradable material that State-level promotes industrialization.
Chain extension method and direct esterification-polycondensation process is mainly contained at present for industrial production poly butylene succinate (PBS).Chain extension method is easy to prepare high molecular weight PBS, but chainextender is toxic material, limits the range of application of PBS; Direct esterification-polycondensation process needs to carry out at high temperature high vacuum condition, the PBS of suitability for industrialized production number-average molecular weight more than 100,000 is difficult to, and the mechanical property of PBS and biological degradability are decided by its molecular weight, current traditional catalyst is as the general shade deviation of the industrialization PBS product (jaundice) of tetrabutyl titanate, due to molecular weight and the color and luster of catalysts influence polymkeric substance, limiting the range of application of PBS, is the big factors that restriction poly butylene succinate is greatly developed.The catalyst selectivity used in current traditional poly butylene succinate PBS production process is poor, Tetrahydrofuran THF growing amount is larger, the low molecule by product that reaction process produces exists the impact of molecular weight comparatively large, and easily causes the generation of the side reactions such as decarboxylation, cyclisation, thermal destruction under comparatively high temps and then affect the important indicator such as form and aspect, limiting viscosity of product.Conventional P BS catalyst efficiency is lower, and PBS polymerization time is longer, is generally more than ten hour.
The catalyzer that current direct esterification-polycondensation process is used for industrial production poly butylene succinate PBS has the titanium/silicon/composite catalyst of phosphorus/metallic compound, composite catalyst of Ti-Sn.The problems such as catalyst preparation process is loaded down with trivial details, repeatability is poor, and prepared PBS product relative molecular weight is lower, product color is poor, preparation time is longer, Tetrahydrofuran THF growing amount is larger.And tin compound toxicity is comparatively large, has strong neurotoxicity, has strong impulse, also have harm to environment, easily cause water pollution to eyes and skin, affect the safety in utilization of PBS product.
Summary of the invention
In order to overcome the above-mentioned defect of prior art, the invention provides a kind of preparation method being suitable for the environment-friendly type titanium-phosphorus coordination composite catalyst of efficient, the highly selective that PBS produces, additionally provide a kind of PBS production method adopting this catalyzer, this catalyzer cost is low, nontoxic, selectivity is good, is conducive to the production efficiency and the quality product that improve PBS.
The technical solution adopted in the present invention is:
Be suitable for a preparation method for the environment-friendly type titanium-phosphorus coordination composite catalyst of efficient, the highly selective that PBS produces, it is characterized in that single stage method prepares titanium-phosphorus coordination composite catalyst with organo phosphorous compounds and organic titanic compound for raw material carries out coordination reaction.
Described Organophosphorous compounds can be in aliphatic phosphate ester, aromatic phosphoric ester, aliphatic phosphites and aromatic series phosphorous acid ester any one or multiple.
Also preferably include BDO in raw materials used, comprise or do not comprise Hinered phenols antioxidant.
The quality proportion optimization of each raw material is: BDO 20 ~ 95 mass parts, organic titanic compound 5 ~ 50 parts, organo phosphorous compounds 5 ~ 50 parts, Hinered phenols antioxidant 0 ~ 30 part.
Can comprising the steps: when there being Hinered phenols antioxidant in raw material, BDO, organo phosphorous compounds and Hinered phenols antioxidant being placed in after reactor is fully uniformly mixed, slowly adding organic titanic compound, and be warming up to 40 ~ 200
oc, reaction 0.5 ~ 12h, obtains homogeneous phase liquid titanium-phosphorus coordination composite catalyst; When there is no Hinered phenols antioxidant in raw material, BDO and organo phosphorous compounds being placed in after reactor is fully uniformly mixed, slowly adding organic titanic compound, and be warming up to 40 ~ 200
oc, reaction 0.5 ~ 12h, obtains homogeneous phase liquid titanium-phosphorus coordination composite catalyst.
Described organic titanic compound can be tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, metatitanic acid four methyl esters, titanium potassium oxalate(T.P.O.), in titanium ethylene glycolate, propylene glycol titanium, butyleneglycol titanium any one or multiple.
Described organo phosphorous compounds can be trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, tricresyl phosphate propyl ester, TNPP tri n pentyl phosphate, tricresyl phosphate isopropyl ester, tributyl phosphate, triphenylphosphate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tripropyl phosphite, three isodecyl phosphite, tri isopropyl phosphorite, trilauryl phosphite, two (octadecyl) pentaerythritol diphosphites, triphenylphosphate, triphenyl phosphite, phenyl diiso decyl phosphorous acid ester, diphenyl isodecyl phosphite, phenyl-bis-(4-octyl phenyl) phosphorous acid ester, three (4-octyl phenyl) phosphorous acid ester, three [(4-octyl group ethylphenyl)] phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, four (2,4-di-tert-butyl-phenyl)-4,4 '-xenyl diphosphites, two diphosphites two (2, the 4-tert-butyl-phenyl) ester of tetramethylolmethane, in two (2,6-di-t-butyl-4-tolyl) pentaerythritol phosphite any one or multiple.
Described Hinered phenols antioxidant can be four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N; N'-is two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine in any one or multiple.
The preparation method of a kind of PBS, with succinic acid and 1,4-butyleneglycol is raw material, under the effect of catalyzer, PBS is formed by esterification and polycondensating process, what described catalyzer adopted any one method for preparing catalyst disclosed by the invention to prepare be suitable for, and that PBS produces is efficient, the environment-friendly type titanium-phosphorus coordination composite catalyst of highly selective, and the mol ratio of the consumption of described catalyzer and the consumption of described succinic acid is preferably 0.01% ~ 3%.
The melting index of the PBS produced is lower than 3g/10min (190 DEG C, 2.16kg), and limiting viscosity reaches 2.05dL/g, number-average molecular weight more than 100,000, and L value >=80, a value >=-0.43, b value≤5.24, colour is much better than Standard.
The invention has the beneficial effects as follows: the present invention utilizes and carries out coordination reaction to organic titanic compounds such as organo phosphorous compounds and titanic acid ester such as aliphatics (Asia) phosphoric acid ester and (or) aromatic series (Asia) phosphoric acid ester, single stage method prepares titanium-phosphorus coordination composite catalyst, preparation flow is short, without " three wastes ", reproducible, and product is nontoxic.The preparation technology of titanium-phosphorus coordination composite catalyst is easy, easy handling, be suitable for large-scale industrial production, mainly solve composite catalyst catalytic efficiency in existing PBS polymerization technique and the problem such as selectivity is lower, preparation process is loaded down with trivial details, repeatability is poor, prepared PBS product relative molecular weight is lower, product color is poor, preparation time is longer, Tetrahydrofuran THF growing amount is larger; For organic titanium series catalysts to the too high problem of the polycondensation catalytic activity of polyester, P contained compound is utilized to carry out ligand complex to titanium atom, utilize the strong coordination of phosphorus atom, change the electronic environment of titanium atom outside, regulate the catalytic activity of titanium, improve the polycondensation selectivity of titanium compound, reduce the side reaction under high temperature, improve polycondensation selectivity, reduce the side reaction in polymerization process, thus improve polycondensation efficiency, product relative molecular weight and color and luster quality, improve the quality of polyester product; Can by regulating the mol ratio of phosphoric and titanium elements, the activity and selectivity of regulation and control catalyzer.The composite catalyst prepared with the present invention carries out PBS production, synthesized by the PBS number-average molecular weight that goes out can reach more than 100,000, limiting viscosity can reach more than 2.05dL/g, and generated time can shorten to 6 hours, and product color is good, security is high.
Accompanying drawing explanation
Fig. 1 is the structural formula of titanium-phosphorus coordination composite catalyst;
Fig. 2 is PBS section photo.
Embodiment
With organic titanic compound, organo phosphorous compounds, Hinered phenols antioxidant (if applying) and 1,4-butyleneglycol is as the titanium-phosphorus coordination composite catalyst described in raw material preparation, by 1 of certain component, 4-butyleneglycol, organo phosphorous compounds and Hinered phenols antioxidant are placed in after reactor is fully uniformly mixed, slowly add organic titanic compound, and being warming up to 40 ~ 200 DEG C, reaction 0.5 ~ 12h, finally obtains homogeneous phase liquid titanium-phosphorus coordination composite catalyst.
In mass parts, described composite catalyst can be made up of following component:
BDO: 20 ~ 95 parts;
Organic titanic compound: 5 ~ 50 parts;
Organo phosphorous compounds: 5 ~ 50 parts;
Hinered phenols antioxidant: 0 ~ 30 part.
In above-mentioned composite catalyst, described organic titanic compound can comprise: tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, metatitanic acid four methyl esters, titanium potassium oxalate(T.P.O.), at least one in titanium ethylene glycolate, propylene glycol titanium, butyleneglycol titanium also can be multiple arbitrarily.Described organo phosphorous compounds can be selected from aliphatics (Asia) phosphoric acid ester or aromatic series (Asia) phosphoric acid ester or aliphatics and aromatic series and share, also other organo phosphorous compoundss can be selected from, aliphatics (Asia) phosphoric acid ester comprises: trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, tricresyl phosphate propyl ester, TNPP tri n pentyl phosphate, tricresyl phosphate isopropyl ester, tributyl phosphate, triphenylphosphate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tripropyl phosphite, three isodecyl phosphite, tri isopropyl phosphorite, trilauryl phosphite, at least one in two (octadecyl) pentaerythritol diphosphites, also can be multiple arbitrarily, aromatic series (Asia) phosphoric acid ester comprises: triphenylphosphate, triphenyl phosphite, phenyl diiso decyl phosphorous acid ester, diphenyl isodecyl phosphite, phenyl-bis-(4-octyl phenyl) phosphorous acid ester, three (4-octyl phenyl) phosphorous acid ester, three [(4-octyl group ethylphenyl)] phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, four (2, 4-di-tert-butyl-phenyl)-4, 4 '-xenyl diphosphites, the two diphosphites two (2 of tetramethylolmethane, 4-tert-butyl-phenyl) ester, two (2, 6-di-t-butyl-4-tolyl) at least one in pentaerythritol phosphite, also can be multiple arbitrarily.(3) oxidation inhibitor is selected from Hinered phenols antioxidant; comprise: four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) at least one in hexanediamine also can be multiple arbitrarily.Described Hinered phenols antioxidant can comprise: four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) at least one in hexanediamine also can be multiple arbitrarily.
Utilize the organo phosphorous compounds such as aliphatics (Asia) phosphoric acid ester and (or) aromatic series (Asia) phosphoric acid ester to carry out coordination reaction with organic titanic compound simultaneously, single stage method prepares titanium-phosphorus coordination composite catalyst, preparation technology's flow process is short, selectivity is high, without " three wastes ", reproducible, and product is nontoxic, safety and environmental protection.Because the polycondensation catalytic activity of organic titanium series catalysts to polyester is too high, consequently leads to the various defects of prior art, the application utilizes P contained compound to carry out ligand complex to titanium atom, to reduce catalytic activity, improve catalytic selectivity, reduce the side reaction in polymerization process, thus improve molecular weight and the quality of polyester product.Utilize the strong coordination of phosphorus atom in organo phosphorous compounds, change the electronic environment of titanium atom outside, regulate the catalytic activity of titanium, improve the polycondensation selectivity of titanium compound, reduce the side reaction under high temperature, thus improve polycondensation efficiency, product relative molecular weight and color and luster.And by regulating the mol ratio of phosphoric and titanium elements, the activity and selectivity of catalyzer can be regulated and controled, make it the different requirements be adapted in reality.Fig. 1 gives the structural formula of titanium-phosphorus coordination composite catalyst.
Here is the embodiment that the present invention prepares described titanium-phosphorus coordination composite catalyst:
Embodiment 1
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 3.0kg1,4-butyleneglycol, 0.8kg tributyl phosphate and 0.4kg tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, stirring makes system mix, in reactor, slowly add 0.8kg tetraethyl titanate, 150 DEG C of reacting by heating 4h, obtain light yellow clear liquid, be called catalyst A.
Embodiment 2
In the 10L reactor that agitator, condenser and temperature sensor are housed; add 2.5kg1; 4-butyleneglycol, 1.2kg triphenylphosphate and 0.3kgN; N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, stir and system is mixed; 1.5kg titanium isopropylate is slowly added in reactor; 180 DEG C of reacting by heating 3h, obtain light yellow clear liquid, are called catalyst B.
Embodiment 3
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 3.2kg1,4-butyleneglycol and 0.4kg trimethyl phosphite 99, stirring makes system mix, 1.4kg tetrabutyl titanate is slowly added in reactor, 50 DEG C of reacting by heating 2h, obtain light yellow clear liquid, are called catalyzer C.
Embodiment 4
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 3.8kg1,4-butyleneglycol, 0.5kg tricresyl phosphate isopropyl ester and 0.4kg triphenyl phosphite, stirring makes system mix, 1.3kg titanium ethylene glycolate is slowly added in reactor, 140 DEG C of reacting by heating 4h, obtain light yellow clear liquid, are called catalyzer D.
Embodiment 5
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 4kg1,4-butyleneglycol, 0.9kg trilauryl phosphite and 0.2kg diphenyl isodecyl phosphite, stirring makes system mix, 1.5kg titanium potassium oxalate(T.P.O.) is slowly added in reactor, 150 DEG C of reacting by heating 3.5h, obtain light yellow clear liquid, are called catalyzer E.
Embodiment 6
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 4kg1,4-butyleneglycol, 1kg phenyl diiso decyl phosphorous acid ester and 0.5kg diphenyl isodecyl phosphite, stirring makes system mix, 1.6kg butyleneglycol titanium is slowly added in reactor, 140 DEG C of reacting by heating 4h, obtain light yellow clear liquid, are called catalyzer F.
Embodiment 7
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 8kg1,4-butyleneglycol, 0.8kg phenyl diiso decyl phosphorous acid ester, 0.4kg diphenyl isodecyl phosphite and 0.5kg phenyl-bis-(4-octyl phenyl) phosphorous acid ester, stirring makes system mix, 0.9kg propylene glycol titanium is slowly added in reactor, 180 DEG C of reacting by heating 3.5h, obtain light yellow clear liquid, are called catalyzer G.
Embodiment 8
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 3kg1,4-butyleneglycol, 1.2kg tri-(4-octyl phenyl) phosphorous acid ester, 1kg phenyl-bis-(4-octyl phenyl) phosphorous acid ester and 0.3kg tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, stirring makes system mix, and slowly adds 1.4kg butyleneglycol titanium in reactor, 120 DEG C of reacting by heating 4.5h, obtain light yellow clear liquid, be called catalyzer H.
Embodiment 9
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 4kg1,4-butyleneglycol, 0.9kg tri-[(4-octyl group ethylphenyl)] phosphorous acid ester, 0.3kg tri-(nonyl phenyl) phosphorous acid ester and 0.5kg tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, stirring makes system mix, in reactor, slowly add 0.5kg titanium ethylene glycolate, 80 DEG C of reacting by heating 7h, obtain light yellow clear liquid, be called catalyst I.
Embodiment 10
In the 10L reactor that agitator, condenser and temperature sensor are housed; add 4kg1; 4-butyleneglycol, 0.6kg tri-(2; 4-di-tert-butyl-phenyl) phosphorous acid, 0.4kg tri-(nonyl phenyl) phosphorous acid ester and 0.4kgN; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine; stirring makes system mix; 0.6kg tetraethyl titanate is slowly added in reactor; 135 DEG C of reacting by heating 5h; obtain light yellow clear liquid, be called catalyzer J.
Embodiment 11
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 4kg1,4-butyleneglycol, 0.4kg two (2,6-di-t-butyl-4-tolyl) two (octadecyl) pentaerythritol diphosphites of pentaerythritol phosphite, 0.4kg tricresyl phosphate isopropyl ester and 0.4kg, stirring makes system mix, and slowly adds 1kg metatitanic acid four methyl esters in reactor, 190 DEG C of reacting by heating 2h, obtain light yellow clear liquid, be called catalyzer K.
Embodiment 12
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 10kg1,4-butyleneglycol, 0.4kg tetramethylolmethane two diphosphites two (2,4-tert-butyl-phenyl) ester, 0.2kg trimethyl phosphite 99 and 0.7kg tetra-(2,4-di-tert-butyl-phenyls)-4,4 '-xenyl diphosphites, stirring makes system mix, in reactor, slowly add 1kg titanium isopropylate, 145 DEG C of reacting by heating 3.5h, obtain light yellow clear liquid, be called catalyzer L.
Embodiment 13
In the 10L reactor that agitator, condenser and temperature sensor are housed, add 6kg1,4-butyleneglycol, 0.2kg tetramethylolmethane two diphosphites two (2,4-tert-butyl-phenyl) ester, 0.5kg tricresyl phosphate isopropyl ester and 0.1kg tetra-(2,4-di-tert-butyl-phenyls)-4,4 '-xenyl diphosphites, stirring makes system mix, in reactor, slowly add 1.4kg titanium isopropylate, 170 DEG C of reacting by heating 3h, obtain light yellow clear liquid, be called catalyzer M.
The titanium prepared by above-described embodiment-phosphorus coordination composite catalyst A-M is used for using succinic acid and butyleneglycol for raw material to be prepared through esterification and polycondensation in the production of PBS as catalyzer, synthesized by the PBS number-average molecular weight that goes out can reach more than 100,000, and product color good (white), security are high.Poly butylene succinate (PBS) melting index that reaction products obtained therefrom is produced is lower than 3g/10min (190 DEG C, 2.16kg), limiting viscosity reaches 2.05dL/g, number-average molecular weight more than 100,000, and L value >=80, a value >=-0.43, b value≤5.24, colour is also far superior to Standard (see Fig. 2), and significantly shortens reaction times to 6 hours.
According to identical mechanism, the titanic acid ester relating to other organo phosphorous compoundss disclosed by the invention and above-described embodiment or do not relate to or other organic titanic compounds that can be used as titanium catalyst carry out coordination reaction, required titanium-phosphorus coordination composite catalyst can be prepared equally, and the strong coordination of phosphorus atom can be utilized equally to change the electronic environment of titanium atom outside, play the catalytic activity regulating titanium, improve the polycondensation selectivity of titanium compound, reduce the side reaction under high temperature, improve polycondensation selectivity, reduce the effect of the side reaction in polymerization process, produce and improve polycondensation efficiency, product relative molecular weight and color and luster quality, improve the technique effect of polyester product quality.
Each preferred and optional technique means disclosed by the invention, unless otherwise indicated and one preferably or alternatives means be outside the further restriction of another technique means, all can arbitrary combination, form some different technical schemes.
Claims (10)
1. one kind is suitable for the preparation method of the environment-friendly type titanium-phosphorus coordination composite catalyst of efficient, the highly selective that PBS produces, it is characterized in that single stage method prepares titanium-phosphorus coordination composite catalyst with organo phosphorous compounds and organic titanic compound for raw material carries out coordination reaction.
2. the preparation method of titanium-phosphorus coordination composite catalyst as claimed in claim 1, it is characterized in that described organo phosphorous compounds be in aliphatic phosphate ester, aromatic phosphoric ester, aliphatic phosphites and aromatic series phosphorous acid ester any one or multiple.
3. the preparation method of titanium-phosphorus coordination composite catalyst as claimed in claim 2, it is characterized in that raw materials used in also comprise BDO, comprise or do not comprise Hinered phenols antioxidant.
4. the preparation method of titanium-phosphorus coordination composite catalyst as claimed in claim 3, it is characterized in that the quality proportioning of each raw material is: BDO 20 ~ 95 mass parts, organic titanic compound 5 ~ 50 parts, organo phosphorous compounds 5 ~ 50 parts, Hinered phenols antioxidant 0 ~ 30 part.
5. the preparation method of titanium-phosphorus coordination composite catalyst as claimed in claim 4, it is characterized in that comprising the steps: when there being Hinered phenols antioxidant in raw material, by 1,4-butyleneglycol, organo phosphorous compounds and Hinered phenols antioxidant are placed in after reactor is fully uniformly mixed, slowly add organic titanic compound, and be warming up to 40 ~ 200
oc, reaction 0.5 ~ 12h, obtains homogeneous phase liquid titanium-phosphorus coordination composite catalyst; When there is no Hinered phenols antioxidant in raw material, BDO and organo phosphorous compounds being placed in after reactor is fully uniformly mixed, slowly adding organic titanic compound, and be warming up to 40 ~ 200
oc, reaction 0.5 ~ 12h, obtains homogeneous phase liquid titanium-phosphorus coordination composite catalyst.
6. the preparation method of the titanium as described in claim 1,2,3,4 or 5-phosphorus coordination composite catalyst, it is characterized in that described organic titanic compound is tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, metatitanic acid four methyl esters, titanium potassium oxalate(T.P.O.), in titanium ethylene glycolate, propylene glycol titanium, butyleneglycol titanium any one or multiple.
7. as claim 1, 2, 3, the preparation method of the titanium described in 4 or 5-phosphorus coordination composite catalyst, is characterized in that described organo phosphorous compounds is trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, tricresyl phosphate propyl ester, TNPP tri n pentyl phosphate, tricresyl phosphate isopropyl ester, tributyl phosphate, triphenylphosphate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tripropyl phosphite, three isodecyl phosphite, tri isopropyl phosphorite, trilauryl phosphite, two (octadecyl) pentaerythritol diphosphites, triphenylphosphate, triphenyl phosphite, phenyl diiso decyl phosphorous acid ester, diphenyl isodecyl phosphite, phenyl-bis-(4-octyl phenyl) phosphorous acid ester, three (4-octyl phenyl) phosphorous acid ester, three [(4-octyl group ethylphenyl)] phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, four (2,4-di-tert-butyl-phenyl)-4,4 '-xenyl diphosphites, two diphosphites two (2, the 4-tert-butyl-phenyl) ester of tetramethylolmethane, in two (2,6-di-t-butyl-4-tolyl) pentaerythritol phosphite any one or multiple.
8. the preparation method of the titanium as described in claim 3,4 or 5-phosphorus coordination composite catalyst; it is characterized in that described Hinered phenols antioxidant is four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and N; N'-is two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine in any one or multiple.
9. the preparation method of a PBS, it is characterized in that with succinic acid and 1,4-butyleneglycol is raw material, under the effect of catalyzer, PBS is formed by esterification and polycondensating process, what described catalyzer adopted the preparation method in claim 1-8 described in any one claim to prepare be suitable for, and that PBS produces is efficient, the environment-friendly type titanium-phosphorus coordination composite catalyst of highly selective, and the mol ratio of the consumption of described catalyzer and the consumption of described succinic acid is 0.01% ~ 3%.
10. PBS preparation method as claimed in claim 9, it is characterized in that the PBS that produces 190 DEG C, melting index under 2.16kg is lower than 3g/10min, limiting viscosity reaches 2.05dL/g, number-average molecular weight more than 100,000, and L value >=80, a value >=-0.43, b value≤5.24, colour is much better than Standard.
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| WO2018113496A1 (en) * | 2016-12-20 | 2018-06-28 | 金发科技股份有限公司 | Pbs resin composition and preparation method therefor |
| CN108484895A (en) * | 2018-04-09 | 2018-09-04 | 福建锦兴环保科技有限公司 | A kind of phosphorus-titanium complex polyester catalyst and its preparation process |
| CN108641069A (en) * | 2018-04-09 | 2018-10-12 | 福建锦兴环保科技有限公司 | A kind of polyester Titanium series catalyst and its preparation process |
| CN113773480A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Catalyst composition for preparing polyglycolide and preparation method of polyglycolide |
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| CN104774320A (en) * | 2015-03-27 | 2015-07-15 | 中国昆仑工程公司 | Composite catalyst and polytrimethylene terephthalate preparation method |
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| JP2004091773A (en) * | 2002-07-12 | 2004-03-25 | Mitsubishi Chemicals Corp | Catalyst for polyester production and process for producing polyester using it |
| CN1962720A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing polyester |
| CN104774320A (en) * | 2015-03-27 | 2015-07-15 | 中国昆仑工程公司 | Composite catalyst and polytrimethylene terephthalate preparation method |
Cited By (7)
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| WO2018113496A1 (en) * | 2016-12-20 | 2018-06-28 | 金发科技股份有限公司 | Pbs resin composition and preparation method therefor |
| US10815332B2 (en) | 2016-12-20 | 2020-10-27 | Kingfa Sci. & Tech. Co., Ltd. | PBS resin composition and preparation method thereof |
| CN108484895A (en) * | 2018-04-09 | 2018-09-04 | 福建锦兴环保科技有限公司 | A kind of phosphorus-titanium complex polyester catalyst and its preparation process |
| CN108641069A (en) * | 2018-04-09 | 2018-10-12 | 福建锦兴环保科技有限公司 | A kind of polyester Titanium series catalyst and its preparation process |
| CN108484895B (en) * | 2018-04-09 | 2020-06-30 | 福建锦兴环保科技有限公司 | Phosphorus-titanium composite polyester catalyst and preparation process thereof |
| CN113773480A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Catalyst composition for preparing polyglycolide and preparation method of polyglycolide |
| CN113773480B (en) * | 2020-06-09 | 2023-06-06 | 中国石油化工股份有限公司 | Catalyst composition for preparing polyglycolide and preparation method of polyglycolide |
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