CN105646570A - Novel organic titanate butanediol titanium, and synthesis method and application thereof - Google Patents
Novel organic titanate butanediol titanium, and synthesis method and application thereof Download PDFInfo
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- CN105646570A CN105646570A CN201610014011.4A CN201610014011A CN105646570A CN 105646570 A CN105646570 A CN 105646570A CN 201610014011 A CN201610014011 A CN 201610014011A CN 105646570 A CN105646570 A CN 105646570A
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- butanediol
- titanium
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- organic titanate
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- KQIQJFPCKQNXSA-UHFFFAOYSA-N butane-1,1-diol;titanium Chemical compound [Ti].CCCC(O)O KQIQJFPCKQNXSA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 14
- -1 1,4-butanediol sodium alkoxide Chemical class 0.000 claims abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 229920000728 polyester Polymers 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 238000010189 synthetic method Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 15
- 239000002244 precipitate Substances 0.000 abstract description 5
- 239000001103 potassium chloride Substances 0.000 abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 19
- 229920001707 polybutylene terephthalate Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a synthesis method of novel organic titanate butanediol titanium. The method comprises the following steps: 1) dissolving solid sodium hydroxide or potassium hydroxide in excessive 1,4-butanediol, and distilling under reduced pressure to remove water generated by reaction, thereby obtaining the 1,4-butanediol sodium alkoxide or potassium alcoholate solution; 2) dropwisely adding titanium tetrachloride into the product obtained in the step 1) in an inert gas atmosphere, and standing after finishing the dropwise addition, thereby generating the sodium chloride or potassium chloride crystal precipitate; and 3) carrying out solid-liquid separation to obtain a yellow transparent butanediol titanium 1,4-butanediol solution, and distilling under reduced pressure to remove 1,4-butanediol, thereby obtaining the white solid which is the target product butanediol titanium. The synthesis method is simple, and the synthesis process is green and environment-friendly. The obtained organic titanate butanediol titanium can be used as a catalyst in esterification and polycondensation reaction of terephthalic acid and 1,4-butanediol, and can also be directly hydrolyzed under proper conditions to prepare nano titanium dioxide.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of novel organotitanium acid esters butanediol titanium and synthetic method thereof and application.
Background technology
At present, the synthesis of polyester engineering plastic master batch in the world, including polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) (PBT) etc., mainly adopting the direct esterification dehydrations such as p-phthalic acid (PTA) and corresponding dihydric alcohol ethylene glycol (EG) or butanediol (BDO) to generate corresponding oligomer, then prepared by the method for the little molecule dihydroxylic alcohols of polycondensation elimination. In the production process of polyester, polycondensation catalyst plays an important role. Current conventional catalyst mainly has antimony system and Titanium series catalyst, wherein Titanium series catalyst, for instance: tetra-n-butyl titanate and tetraisopropyl titanate, with it, activity is high, toxicity is little and enjoys favor. But the hydrolytic stability of tetra-n-butyl titanate and tetraisopropyl titanate is poor, polyester synthesis initial stage due to esterification dehydration, catalyst and water react meeting loss of catalytic activity, so cause that catalyst amount increases, increase metal-oxide content in polyester master particle simultaneously, have influence on the quality of polyester. Therefore, synthesizing new Titanium series catalyst is always up a study hotspot of Ge great polyester company in the world in recent years.
The present invention is raw material based on the polymerization single polymerization monomer BDO and titanium tetrachloride of PBT, has synthesized a kind of Novel Titanium acid esters butanediol titanium by improveing Ni Laisi method. This novel organotitanium acid esters acts not only as polyester synthesis catalyst, it is also possible to be used as preparing the presoma of nano titanium oxide, has important use value and is widely applied prospect.
Summary of the invention
Present invention aim to overcome that prior art defect, it is provided that a kind of novel organotitanium acid esters butanediol titanium and synthetic method thereof and application.
For achieving the above object, the present invention adopts the following technical scheme that
The synthetic method of a kind of novel organotitanium acid esters butanediol titanium, it comprises the steps:
1) solid sodium hydroxide or potassium hydroxide are dissolved in excessive BDO, then remove the water that reaction generates under reduced pressure, it is thus achieved that the sodium alkoxide of BDO or potassium alkoxide solution;
2) under atmosphere of inert gases, titanium tetrachloride is dropped in step 1) products therefrom, dropwise, stand, make sodium chloride or the potassium chloride salt crystalline deposit of generation;
3) by the technology solid-liquid separation such as sucking filtration or centrifugation that reduces pressure, obtain the BDO solution of the butanediol titanium of yellow transparent, remove BDO under reduced pressure, obtain white solid, be target product butanediol titanium. The molecular formula of butanediol titanium is Ti (OCH2CH2CH2CH2O)2, have a structure that
��
In above-mentioned synthetic method, previously prepared sodium alkoxide or potassium alcoholate (reaction 1), then generate target product (reaction 2) with the sodium alkoxide of titanium tetrachloride and preparation or alcohol nak response. Concrete reactional equation is as follows:
��
Concrete, the condition removing the water that reaction generates in step 1) under reduced pressure is: temperature 50-100 DEG C, absolute pressure 1.33-51.33kPa. Remove under reduced pressure and process can be kept stirring for speed at about 200r/min. In step 1), the addition of BDO to substantially exceed theoretical response magnitude, and it had both served as reactant and has also functioned as solvent, and otherwise the reaction later stage can generate gel, it is impossible to separates and obtains target product butanediol titanium. Sodium hydroxide or potassium hydroxide to be dissolved completely in BDO, and the molar ratio of sodium hydroxide or potassium hydroxide and BDO is 1:2-4.
Concrete, step 2) in the process of dropping titanium tetrachloride, control temperature less than 20 DEG C. Dropping process is kept stirring for speed dropwise in about 300r/min, 3h. During dropping titanium tetrachloride, also otherwise open close enter nitrogen or noble gas, to avoid being mixed into of steam to react with titanium tetrachloride. Titanium tetrachloride is added with the ratio that mol ratio is 1:4 of sodium hydroxide or potassium hydroxide according to it.
1,4 butanediol solutions of the butanediol titanium that step 3) obtains can be used as the polycondensation catalyst of polyester after being diluted to finite concentration further with 1,4-butanediol; Can also directly under proper condition hydrolysis prepare nano titanium oxide.
Adopt the organic titanate butanediol titanium that arbitrary said method is synthetically derived.
Above-mentioned organic titanate butanediol titanium as catalyst polyester synthesis react in application.
Above-mentioned organic titanate butanediol titanium as catalyst polyester synthesis react in application, concrete, it is possible to be: organic titanate butanediol titanium is applied in p-phthalic acid and the esterification of BDO, polycondensation reaction as catalyst.
Compared to the prior art, beneficial effects of the present invention:
The present invention is by improveing Ni Laisifa, it is possible to the BDO solution of the fairly simple convenient butanediol titanium preparing various concentration and two kinds of products of pure butanediol titanium. This method raw material BDO, titanium tetrachloride, sodium hydroxide and potassium hydroxide are cheap and easy to get, the 1 of product butanediol titanium, 4-butanediol solution and pure butanediol titanium both can serve as catalyst, may be used for again preparing nano titanium oxide, added value is high, has huge economic benefit. And adopting synthetic method of the present invention to produce butanediol titanium, do not produce spent acid waste gas etc. in course of reaction, by-product is sodium chloride or potassium chloride, environmental protection, therefore has important actual application value.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is discussed in detail further, but protection scope of the present invention is not limited thereto.
Embodiment 1
Sodium hydroxide 160g is joined in the stainless steel cauldron with agitating device, is then injected into BDO and is about 721g;Reactor is warming up to 50 DEG C of stirred reaction mixtures makes sodium hydroxide all dissolve, open vacuum pump and control in reactor absolute pressure close to 1.33kPa, the water generated in reactor is made to seethe with excitement and steam system, boiling is stopped and after anhydrous steam steams again Deng reactant liquor, close vacuum pump and in reactor, be slowly added dropwise titanium tetrachloride be under agitation about in 190g(dropping process and control temperature less than 20 DEG C), after dropwising, standing makes the Sodium chloride deposit that reaction produces. Decompression sucking filtration reaction mixture, obtains the BDO solution of the clarification butanediol titanium of yellow transparent after isolating sodium chloride. The 1 of butanediol titanium will obtained, 4-butanediol solution is when 150 DEG C of about absolute pressure 5kPa, decompression steams most solvent 1,4-butanediol, the butanediol titanium solid of white can precipitate out bottom reactor, leach target product and namely it is obtained pure butanediol titanium valve body (sample one), productivity about 99.1% 200 DEG C of decompressing and extracting.
3L pet reaction still adds 830g p-phthalic acid, 1000g1,4-butanediol, 0.15g sample one (butanediol titanium), obtaining polyester sample PBT through 200 DEG C of esterification 3h and 240 DEG C of polycondensation reaction 2h, melt flow rate 29.5g/10min, b value is 2.2.
1. the mensuration of melt flow rate (MFR): take a small amount of PBT and put under infrared lamp dried, fill 2/3 with material barrel, at 250 DEG C, put in melt-flow instrument, compress, preheating 5min, plus the power of 26.24N on barrel, material flows out, after the amount flowed out is uniform, cut the material in 10s some, calculate average magnitude, be xg/10s. Xg/10s=60xg/10min. Its numerical value is more little shows that the relative molecular mass of product is more high.
2. the mensuration of whiteness: take a small amount of PBT and add people to WSC-S colour examining colour-difference-metre, measure the whiteness of PBT product. Wherein b value is more little shows that the color and luster of product is more good.
Embodiment 2
Sodium hydroxide 500g is joined in stainless steel cauldron, is then injected into BDO and is about 3380g; Reactor is warming up to 100 DEG C of stirred reaction mixtures makes sodium hydroxide all dissolve, open vacuum pump and control slight negative pressure in reactor, the water generated in still is made to seethe with excitement and steam system, boiling is stopped and after anhydrous steam steams again Deng reactant liquor, close vacuum pump and in reactor, be slowly added dropwise titanium tetrachloride be under agitation about in 593g(dropping process and control temperature less than 20 DEG C), after dropwising, standing makes the Sodium chloride deposit that reaction produces. By centrifuge separating reaction mixed liquor, after isolating sodium chloride, obtain the BDO solution of the clarification butanediol titanium of yellow transparent. The 1 of butanediol titanium will obtained, 4-butanediol solution is when 170 DEG C of about absolute pressure 10kPa, decompression steams most solvent 1,4-butanediol, the butanediol titanium of white can precipitate out automatically bottom reactor, leach target product and namely it is obtained pure butanediol titanium valve body (sample two), productivity about 98.5% 200 DEG C of decompressing and extracting.
3L pet reaction still adds 830g p-phthalic acid, 1000g1,4-butanediol, 0.22g sample two (butanediol titanium), obtaining polyester sample PBT through 200 DEG C of esterification 3h and 240 DEG C of polycondensation reaction 2h, melt flow rate 27.1g/10min, b value is 2.1.
Embodiment 3
Potassium hydroxide 500g is joined in stainless steel cauldron, is then injected into BDO and is about 3212g;Reactor is warming up to 70 DEG C of stirred reaction mixtures makes potassium hydroxide all dissolve, open vacuum pump and control in still absolute pressure close to 10kPa, the water generated in still is made to seethe with excitement and steam system, boiling is stopped and after anhydrous steam steams again Deng reactant liquor, close vacuum pump and be slowly added dropwise in reactor under agitation titanium tetrachloride be about in 423g(dropping process control temperature less than 20 DEG C), drip stand make reaction produce potassium chloride precipitate. Decompression sucking filtration reaction mixture, obtains the BDO solution of the clarification butanediol titanium of yellow transparent after isolating potassium chloride. The 1 of butanediol titanium will obtained, 4-butanediol solution is when 130 DEG C of about absolute pressure 2kPa, decompression steams most solvent 1,4-butanediol, the butanediol titanium of white can precipitate out automatically bottom reactor, leach target product and namely it is obtained pure butanediol titanium valve body (sample three), productivity about 99.3% 200 DEG C of decompressing and extracting.
3L pet reaction still adds 830g p-phthalic acid, 1000g1,4-butanediol, 0.36g sample three (butanediol titanium), obtaining polyester sample PBT through 200 DEG C of esterification 3h and 240 DEG C of polycondensation reaction 2h, melt flow rate 28.9g/10min, b value is 2.4.
Comparative example 1
Adding 830g p-phthalic acid, 1000g1,4-butanediol, 0.36g butyl titanate in 3L pet reaction still, obtain polyester sample PBT through 200 DEG C of esterification 3h and 240 DEG C of polycondensation reaction 2h, melt flow rate 31.9g/10min, b value is 2.7.
Above-described embodiment shows: the novel organotitanium acid esters catalyst of the butanediol titanium of the alcohol alkali exchange process synthesis that the present invention adopts, the melt flow rate of catalysis gained polyester product and whiteness are better than traditional Titanium series catalyst (butyl titanate).
Claims (6)
1. the synthetic method of a novel organotitanium acid esters butanediol titanium, it is characterised in that comprise the steps:
1) solid sodium hydroxide or potassium hydroxide are dissolved in excessive BDO, then remove the water that reaction generates under reduced pressure, it is thus achieved that the sodium alkoxide of BDO or potassium alkoxide solution;
2) under atmosphere of inert gases, titanium tetrachloride is dropped in step 1) products therefrom, dropwise, stand, make sodium chloride or the potassium chloride salt crystalline deposit of generation;
3) solid-liquid separation, obtains the BDO solution of the butanediol titanium of yellow transparent, removes BDO under reduced pressure, obtain white solid, is target product butanediol titanium.
2. the synthetic method of novel organotitanium acid esters butanediol titanium as claimed in claim 1, it is characterised in that the condition removing the water that reaction generates in step 1) under reduced pressure is: temperature 50-100 DEG C, absolute pressure 1.33-51.33kPa.
3. the synthetic method of as claimed in claim 1 novel organotitanium acid esters butanediol titanium, it is characterised in that step 2) in the process of dropping titanium tetrachloride, control temperature less than 20 DEG C.
4. adopt the organic titanate butanediol titanium that the arbitrary described method of claims 1 to 3 is synthetically derived.
5. organic titanate butanediol titanium described in claim 4 as catalyst polyester synthesis react in application.
6. as claimed in claim 5 organic titanate butanediol titanium as catalyst application in polyester synthesis is reacted, it is characterised in that organic titanate butanediol titanium is applied in p-phthalic acid and the esterification of BDO, polycondensation reaction as catalyst.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510747484 | 2015-11-06 | ||
| CN2015107474840 | 2015-11-06 |
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| CN105646570A true CN105646570A (en) | 2016-06-08 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348319A (en) * | 2015-12-02 | 2016-02-24 | 河南开祥精细化工有限公司 | Titanium butanediol and preparation method thereof |
| CN112723580A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Method for reducing chlorine content in chlorine-containing organic waste liquid and method for treating chlorine-containing organic waste liquid |
| CN114075237A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of titanium dialkoxide |
| CN114075238A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of tetra-butylene titanate |
| CN114380664A (en) * | 2022-01-25 | 2022-04-22 | 浙江圣安化工股份有限公司 | Alkali metal polyol salt and preparation method thereof |
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- 2016-01-11 CN CN201610014011.4A patent/CN105646570A/en active Pending
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| CN1403464A (en) * | 2002-10-15 | 2003-03-19 | 上海交通大学 | Prepn of dibasic alkoxide of titanium |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348319A (en) * | 2015-12-02 | 2016-02-24 | 河南开祥精细化工有限公司 | Titanium butanediol and preparation method thereof |
| CN112723580A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Method for reducing chlorine content in chlorine-containing organic waste liquid and method for treating chlorine-containing organic waste liquid |
| CN114075237A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of titanium dialkoxide |
| CN114075238A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of tetra-butylene titanate |
| CN114075238B (en) * | 2020-08-19 | 2023-11-17 | 中国石油化工股份有限公司 | Preparation method of tetrabutyl glycol titanate |
| CN114075237B (en) * | 2020-08-19 | 2024-01-19 | 中国石油化工股份有限公司 | Preparation method of titanium diol |
| CN114380664A (en) * | 2022-01-25 | 2022-04-22 | 浙江圣安化工股份有限公司 | Alkali metal polyol salt and preparation method thereof |
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Application publication date: 20160608 |