CN103087089B - Organic titanic compound and compound thereof and preparation method - Google Patents
Organic titanic compound and compound thereof and preparation method Download PDFInfo
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- CN103087089B CN103087089B CN201310009209.XA CN201310009209A CN103087089B CN 103087089 B CN103087089 B CN 103087089B CN 201310009209 A CN201310009209 A CN 201310009209A CN 103087089 B CN103087089 B CN 103087089B
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Abstract
The invention provides a kind of organic titanic compound and compound thereof, and the preparation method of this compound and compound. The general structure of described organic titanic compound is Tix(OR1O)y(OOCC6H4COO)zH4. The decentralized photo of the compound of described organic titanic compound is above-mentioned organic titanic compound. With titanate esters, binary aliphatic alcohol and para-C6H4(COOR2)2For raw material reaction, after collecting, separation can make respectively organic titanic compound and compound thereof. Organic titanic compound structure uniqueness provided by the invention, easily peels off as laminar structured and be scattered in composite matrix with laminated structure, and this specific character has been brought a series of superior functions and function. Preparation method's raw material of this compound provided by the invention and compound thereof is easy to get simultaneously, easy and simple to handle, is applicable to industrialization promotion. Therefore, this organic titanic compound and compound thereof have important academic significance and potential commercial value.
Description
Technical field
The present invention relates to a kind of organic titanic compound and compound thereof, and the preparation side of this compound and compoundMethod.
Background technology
Titanium is that on the earth, reserves occupy the metal of the 4th, estimates that effective storage capacity is 300,000,000 tons. As everyone knows, titaniumProduct is owing to having not corrosion (seawater corrosion resistance completely), light weight (density 4.51g/cm3), tensile strength is highFeatures such as (280～1600MPa), conventionally with titanium oxide powder and titanium series organic compound, as the form of titanate estersBe widely used.
Titanium series organic compound be mainly used as catalyst, curing agent, also can be used as surfactant, dispersant,Water repellent agent or antirust agent etc., synthetic method mainly contains sol-gel process, Nelles method etc.
Xu Hong, Huang Wei, Cheng Cunkang, Gu Hongchen. the preparation of titanium ethylene glycolate and in polycondensation of polyester catalysis and original positionApplication during function is compound. China YouSe Acta Metallurgica Sinica, 2004,14(3): 221-227 bibliographical information,The classical Nelles method of the employings such as Gu Hongchen has been synthesized titanium ethylene glycolate catalyst, and structural formula is Ti(OCH2CH2O)2; Cao Shanwen, Li Chaohui, development and the prospect of the .PET of Fu Le army polycondensation catalyst. polyesterIndustry, 2004,17(5): 5-9 bibliographical information, Cao of the positive vast and boundless chemical fibre new material of Jinan, Shandong Province Co., Ltd is kindThe people such as literary composition adopt hydrolysis oxidation combination technique nano grade titanium series catalysts; 5 green grass or young crops of China Petrochemical CorporationPrepared a kind of metallocene titanium compound of new structure Deng people, its general formula is R1Ti(OCH2R2)3, R in formula1For cyclopentadienyl group, substituted cyclopentadienyl, R2For the aromatic hydrocarbon group containing 6 ~ 20 carbon atoms. This changeThe catalyst of compound and alkylaluminoxane composition can be used for preparing the poly styrene polymer of normality between height, and toolThere are catalytic activity, feature that catalytic efficiency is high, can be used in industrial production.
Summary of the invention
The invention provides a kind of organic titanic compound and compound thereof, and the preparation of this compound and compoundMethod.
The general structure of organic titanic compound of the present invention is as follows:
Tix(OR1O)y(OOCC6H4COO)zH4
Wherein R1For C2~C4Alkyl, x >=1, z >=1 and 2y+2z=4x+4.
Further, x=4 in the general structure of described organic titanic compound.
Further, the general structure of described organic titanic compound is Ti4(OR1O)8(OOCC6H4COO)2H4。
From described general formula, described organic titanic compound at least comprises a benzene ring structure, and comprises alkoxylTitanium key and acyl group titanium key, for example, shown in following formula (I) structure, this structure, only for illustrating, does not have and appointsWhat directive property:
Further, described organic titanic compound is lamellar structure, peelable one-tenth nano-grade structure.
The present invention also provides the preparation method of above-mentioned organic titanic compound, and it comprises the following steps:
11) raw material is mixed, at 100 ~ 300 DEG C, under 0 ~ 0.4MPa meter pressure, react esterification or esterCessation reaction when exchange degree reaches 10% ~ 100%;
12) separated and collected organic titanic compound from reaction system;
Described meter pressure is called again relative pressure, and the pressure that Pressure gauge shows refers to the true of device interior somewhereDifference between real pressure and atmospheric pressure.
Described raw material comprises titanate esters, binary aliphatic alcohol and para-C6H4(COOR2)2, wherein R2Be selected from hydrogen,Methyl or ethyl.
Described esterification or ester exchange degree refer to binary aliphatic alcohol and para-C in raw material6H4(COOR2)2Esterification orThe reaction conversion ratio of ester exchange.
Further, described step 11) staged reaction, is specifically included in 150 ~ 180 DEG C of temperature control reaction 0.5 ~ 1.5hAfter, be warming up to 200 ~ 280 DEG C and continue reaction.
Further, the preferred tetrabutyl titanate of described titanate esters, tetraisopropyl titanate or tetraethyl titanate.
Further, the preferred ethylene glycol of described binary aliphatic alcohol (EG), 1,3-PD (PDO) or Isosorbide-5-Nitrae-Ding bis-Alcohol (BD).
Further, described separation method is that reaction system adds phenol tetrachloroethane solution, and insoluble matter is organic titaniumCompound.
Further, described esterification or ester exchange degree are followed the tracks of by collecting distillate, and described distillate comprisesThe alcohol that titanate esters reaction produces and the product of esterification or ester exchange.
Further, described distillate is water and C1~C4More than one in fatty alcohol.
The present invention also provides a kind of compound of organic titanic compound, and the decentralized photo of described compound is above-mentionedly to haveMachine titanium compound.
Further, the continuous phase of described compound is one in terephthalic acid (TPA) (PTA) and terephthalateMore than kind.
Further, described terephthalate is dimethyl terephthalate (DMT) (DMT), terephthalic acid (TPA) diethylEster, bishydroxyethyl terephthalate (BHET), the two hydroxypropyl acrylates (BHPT) of terephthalic acid (TPA) and terephthaldehydeMore than one in the two hydroxy butyl esters (BHBT) of acid.
The present invention also provides the compound preparation method of above-mentioned organic titanic compound, and it comprises the following steps:
21) raw material is mixed, at 100 ~ 300 DEG C, under 0 ~ 0.4MPa meter pressure, react esterification or esterCessation reaction when exchange degree reaches 10% ~ 100%;
22) reaction system is cooling, and collecting solid matter is the compound of organic titanic compound;
Described raw material comprises titanate esters, binary aliphatic alcohol and para-C6H4(COOR2)2, wherein R2Be selected from hydrogen,Methyl or ethyl.
Further, described step 21) staged reaction, be specifically included in 150 ~ 180 DEG C of temperature control reaction 0.5 ~ 1.5hAfter, be warming up to 200 ~ 280 DEG C and continue reaction.
Further, the preferred tetrabutyl titanate of described titanate esters, tetraisopropyl titanate or tetraethyl titanate.
Further, the preferred ethylene glycol of described binary aliphatic alcohol (EG), 1,3-PD (PDO) or Isosorbide-5-Nitrae-DingGlycol (BD).
Further, described esterification or ester exchange degree are followed the tracks of by collecting distillate, and described distillate comprisesThe alcohol that titanate esters reaction produces and the product of esterification or ester exchange.
Further, described distillate is water and C1~C4More than one in fatty alcohol.
Organic titanic compound structure uniqueness provided by the invention, easily peels off as laminar structured and divide with laminated structureFall apart in polymeric matrix, this specific character has been brought a series of superior functions and function, such as can be used as functionAnti ultraviolet agent additive or far infrared transmission additive etc. in macromolecular material, especially when it is peeled off as nanoscaleWhen laminated structure, performance is more outstanding. The preparation side of this compound provided by the invention and compound thereof simultaneouslyMethod raw material is easy to get, easy and simple to handle, is applicable to industrialization promotion. Therefore, this organic titanic compound and compound thereofThere is important academic significance and potential commercial value.
Brief description of the drawings
Fig. 1 is the SEM photo of organic titanic compound described in embodiment 1.
Detailed description of the invention
Tester:
1, Nicolet-20sx-B type infrared spectrometer, KBr pressed disc method, scanning 400～4000cm-1。
2, Japanese JSM-5600LV type SEM, amplifies 5000～20000 times.
3, the Avance400 of Bruker company type nuclear magnetic resonance chemical analyser test13C-MASNMR。
4, BrukerUltraflex III TOF/TOF type mass spectrograph, records substance assistant laser desorpted/ionogenSpectrum (MALDI-TOF-MS).
Embodiment 1
23g tetrabutyl titanate is added to 498g(1eq) terephthalic acid (TPA) and 279g(1.5eq) ethylene glycol,Be under 0.1MPa meter pressure at initial pressure, after 150 DEG C of left and right temperature control reaction 1.2h, be warming up to 260 DEG C of left sidesRight continuation reaction. Collect the liquid distillating in esterification reaction process, when the molal quantity of water is wherein terephthaldehydeAcid 2 times time (degree of esterification approximately 100%), cessation reaction.
1) reaction system is cooling, collects solid wherein, is the compound containing organic titanic compound. Described haveMachine titanium compound is dispersed in the matrix of BHET with laminated structure.
2) dissolve composite matrix material with the phenol tetrachloroethane solution of 1:1 weight ratio, centrifugation, collectsInsoluble matter is organic titanic compound. Described compound is that nano-grade structure is disperseed, referring to Fig. 1.
Embodiment 2 ~ 7 preparation method's reference examples 1, the concrete condition of each embodiment and the results are shown in Table 1:
Table 1 embodiment 1 ~ 7
The organic titanic compound FTIR of embodiment 1 ~ 7 is at 1125cm-1There is the absworption peak of Ti-O-C, saidBright compound comprises alkoxytitanium key and acyl group titanium key;
The organic titanic compound of embodiment 1 ~ 713In C-MASNMR, 120-140ppm is the change of carbon on phenyl ringDisplacement study, illustrates that compound comprises benzene ring structure.
Any organic titanic compound of preparing in embodiment 1-7 or its compound are passed through to in-situ polymerization or meltingBlending method is added in PET, only needs the organic titanic compound content of 0.3wt% in the function PET material of preparation,Its ultraviolet shielding rate (UPF) can reach 51.4 ~ 72, and test condition is: TU-1901Lambda950, wavelengthScope is 280-400nm; JPS-5X far infrared emissivity tester test far infrared normal emittance reaches85-89%。
The above be only the specific embodiment of the present invention, but protection scope of the present invention is not limited toThis, any be familiar with those skilled in the art the present invention disclose technical scope in, can expect easilyChange or replace, within all should being encompassed in protection scope of the present invention.
Claims (12)
1. an organic titanic compound, is characterized in that, described organic titanic compound is lamellar structure, described organic titaniumCompound has general formula (I) structure:
The preparation method of described organic titanic compound comprises the following steps:
11) raw material is mixed, staged reaction, is specifically included in 150～180 DEG C of temperature control reactionsAfter 0.5～1.5h, be warming up to 200～280 DEG C continue reaction, under 0～0.4MPa meter pressure, react, esterification orCessation reaction when ester exchange degree reaches 10%～100%;
12) separated and collected organic titanic compound from reaction system; Described raw material comprises titanate esters, binary fatFat alcohol and para-C6H4(COOR2)2, wherein R2Be selected from hydrogen, methyl or ethyl.
2. a kind of organic titanic compound according to claim 1, is characterized in that, described lamellar structure is nanometerLevel lamellar structure.
3. a kind of preparation method of organic titanic compound described in claim 1 or 2, is characterized in that, comprises following stepRapid:
11) raw material is mixed, staged reaction, is specifically included in 150～180 DEG C of temperature control reactionsAfter 0.5～1.5h, be warming up to 200～280 DEG C continue reaction, under 0～0.4MPa meter pressure, react, esterification orCessation reaction when ester exchange degree reaches 10%～100%;
12) separated and collected organic titanic compound from reaction system; Described raw material comprises titanate esters, twoUnit's fatty alcohol and para-C6H4(COOR2)2, wherein R2Be selected from hydrogen, methyl or ethyl.
4. a kind of preparation method of organic titanic compound according to claim 3, is characterized in that described esterificationOr ester exchange degree follows the tracks of by collecting distillate, described distillate comprises what titanate esters reaction producedThe product of alcohol and esterification or ester exchange.
5. a kind of preparation method of organic titanic compound according to claim 4, is characterized in that described metatitanic acidEster is tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate.
6. a kind of preparation method of organic titanic compound according to claim 4, is characterized in that described binaryFatty alcohol is ethylene glycol, 1,3-PD or BDO.
7. a compound for organic titanic compound, is characterized in that, the decentralized photo of described compound is claim 1Or a kind of organic titanic compound described in 2, the continuous phase of described compound is terephthalic acid (TPA) and terephthalateIn more than one.
8. a kind of compound of organic titanic compound according to claim 7, is characterized in that, described to benzene twoFormic acid esters is dimethyl terephthalate (DMT), diethyl terephthalate, bishydroxyethyl terephthalate, rightMore than one in the two hydroxypropyl acrylates of phthalic acid and the two hydroxy butyl esters of terephthalic acid (TPA).
9. a kind of preparation method of compound of organic titanic compound described in claim 7 or 8, is characterized in that, comprisesFollowing steps:
21) raw material is mixed, staged reaction, is specifically included in 150～180 DEG C of temperature control reactionsAfter 0.5～1.5h, be warming up to 200～280 DEG C and continue reaction, under 0～0.4Mpa meter pressure, react esterCessation reaction when change or ester exchange degree reach 10%～100%;
22) reaction system is cooling, and collecting solid matter is the compound of organic titanic compound; Described formerMaterial comprises titanate esters, binary aliphatic alcohol and para-C6H4(COOR2)2, wherein R2Be selected from hydrogen, methyl orEthyl.
10. a kind of preparation method of compound of organic titanic compound according to claim 9, is characterized in that,Described esterification or ester exchange degree are followed the tracks of by collecting distillate, and described distillate comprises that titanate esters is anti-The product of the alcohol that should produce and esterification or ester exchange.
11. a kind of preparation methods of compound of organic titanic compound according to claim 10, is characterized in that,Described titanate esters is tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate.
12. a kind of preparation methods of compound of organic titanic compound according to claim 10, is characterized in that,Described binary aliphatic alcohol is ethylene glycol, 1,3-PD or BDO.
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Effective date of registration: 20200330 Address after: 201499 workshop 1, building 34, No. 38, SHUNGONG Road, Fengxian District, Shanghai Patentee after: Shanghai Huiyi New Material Technology Co., Ltd Address before: 201620 Shanghai, North Renmin Road, Songjiang District, No. 2999 Patentee before: DONGHUA University |
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