CN101235049A - Titanium series organic compound material and its preparation and application - Google Patents
Titanium series organic compound material and its preparation and application Download PDFInfo
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- CN101235049A CN101235049A CNA2008100341481A CN200810034148A CN101235049A CN 101235049 A CN101235049 A CN 101235049A CN A2008100341481 A CNA2008100341481 A CN A2008100341481A CN 200810034148 A CN200810034148 A CN 200810034148A CN 101235049 A CN101235049 A CN 101235049A
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Abstract
The invention provides a titanium organic compound material, a corresponding preparation method and an application. The preparation method comprises synthesizing titanium sol, mixing titanium sol with polyatomic alcohol materials, adding dicarboxylic acids material to process refluxing reaction with the esterification reaction system of the polyatomic alcohol materials to obtain esterified ester/titanium organic compound composite material, centrifugally separating the composite material or dissolving the composite material via solvent and separating centrifugally to obtain titanium organic compound. The titanium organic compound and esterified ester/titanium organic compound composite material can be used as catalyst synthesized from polyester, ultraviolet shield additive and high polymer modified additive, which is leaded into high polymer system via blending or in-situ polymerization to provide high polymer substrate ultraviolet shield function and adjust shaping processing property. The esterified ester/titanium organic compound composite material can be synthesized into polyester/titanium organic compound composite material via polycondensation reaction, whose formula is represented as above.
Description
Technical field
The present invention relates to a kind of titanium series organic compound and preparation method thereof.
Background technology
Titanium is that reserves occupy the 4th metal on the earth, estimates that effective storage capacity is 300,000,000 tons.As everyone knows, titanium products is owing to have not corrosion (seawater corrosion resistance fully), light weight (density 4.51g/cm
3), (characteristics such as 280～1600MPa) usually with titanium oxide powder and titanium series organic compound, are widely used as the form of titanium alkoxide the tensile strength height.
Titanium series organic compound mainly be used as catalyzer, solidifying agent, also useful as surfactants, dispersion agent, water repellent agent or rust-preventive agent etc., synthetic method mainly contains sol-gel method, Nelles method etc.Xu Hong, Huang Wei, Cheng Cunkang, Gu Hongchen. the preparation of titanium ethylene glycolate and the application in polycondensation of polyester catalysis and former bit function are compound thereof. the China YouSe Acta Metallurgica Sinica, 2004,14 (3): the 221-227 bibliographical information, the classical Nelles method of employings such as Gu Hongchen has been synthesized the titanium ethylene glycolate catalyzer, and structural formula is Ti (OCH
2CH
2O)
2Cao Shanwen, Li Chaohui, the development and the prospect of paying the happy .PET of army polycondensation catalyst. polyester industrial, 2004,17 (5): the 5-9 bibliographical information, the people such as Cao Shanwen of Shandong Jinan Zhenghao Chemical Fiber New Material Co., Ltd. adopt hydrolysis oxidation combination technique nano grade titanium series catalysts; People such as the Wu Qing of China PetroChemical Corporation have prepared a kind of metallocene titanium compound of novel texture, and its general formula is R
1Ti (OCH
2R
2)
3, R in the formula
1Be cyclopentadienyl, substituted cyclopentadienyl, R
2For containing the aromatic hydrocarbon group of 6～20 carbon atoms.The catalyzer that this compound and alkylaluminoxane are formed can be used for preparing normal poly styrene polymer between height, and has catalytic activity, characteristics that catalytic efficiency is high, can be used in the industrial production.
The compound of synthetic new titanium to expand the purposes of titanium, is the problem that relevant field is extremely paid close attention to.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of titanium series organic compound material and its production and application, to satisfy the needs of the parties concerned.
The general structure of titanium series organic compound of the present invention is as follows:
Wherein:
R
1Be C
xH
yO
z, x=2～18, y=2～36, z=0～1, and be integer;
R
2Be C
xH
y, x=2～18, y=2～36, and be integer;
R
3Be C
xH
yO
z, x=0～2000 and be integer, y=1～4000 and be integer, z=1～800 and be integer.
The preparation method of above-mentioned titanium series organic compound comprises the steps:
Titanium colloidal sol is mixed with polyvalent alcohol matter, add di-carboxylic acid then, backflow esterification under 100-300 ℃ of temperature and the 0-0.6Mpa pressure, collect distilled liquid in the esterification reaction process, when the mole number of distillate termination reaction when being 0.20-4.0 times of used di-carboxylic acid class material, obtain carboxylate/titanium series organic compound matrix material, with the direct centrifugation of this matrix material, or, can obtain titanium series organic compound with centrifugation after the dissolution with solvents;
Proportioning raw materials in the reaction system:
0.01≤D≤0.5; D=di-carboxylic acid/polyvalent alcohol, mol ratio;
The amount of used titanium colloidal sol is that wherein the amount of titanium component is 0.1～50% of a di-carboxylic acid molar weight.
The chemical structure of general formula of said polyvalent alcohol is as follows:
HO-C
x1H
y1O
z1-OH；
Wherein:
X1=2～18, y1=2～36 and z1=0～1 and be integer;
Preferred polyhydric alcohols is with ethylene glycol, 1, ammediol, 1,4-butyleneglycol, neopentyl glycol, TriMethylolPropane(TMP), 2, one or more in 2-dimethylol propionic acid or the hexylene glycol;
The chemical structure of general formula of said di-carboxylic acid is as follows:
R
5OC-C
x2H
y2-COR
5；
X2=2～18, y=2～36 and be integer;
R
5Be Cl, Br or C
mH
nO, m=0～18 wherein, n=1～36, and be integer.
Di-carboxylic acid is preferably terephthalic acid, m-phthalic acid, phthalic acid, to naphthalic acid, between naphthalic acid, adjacent naphthalic acid, dimethyl terephthalate (DMT), diethyl terephthalate, dimethyl isophthalate, dimethyl isophthalate, dimethyl phthalate, diethyl phthalate, to naphthalene diformic acid dimethyl ester, to the naphthalic acid diethyl ester, between naphthalene diformic acid dimethyl ester, between the naphthalic acid diethyl ester, adjacent naphthalene diformic acid dimethyl ester, adjacent naphthalic acid diethyl ester, in m-phthalic acid or the hexanodioic acid one or more;
The preparation method of said titanium colloidal sol is as follows:
Solvent, water and sequestrant wiring solution-forming A with cumulative volume 20%-60%;
The titanium alkoxide is under agitation splashed in the solvent of surplus wiring solution-forming B;
Solution A is splashed into solution B, and the pH of regulation system refluxes and stirs 0.5～5h at 4-6.5, obtains the titanium colloidal sol of homogeneous transparent; The content of titanium is 0.03-25wt% in the obtained titanium colloidal sol.
Said titanium alkoxide chemistry skeleton symbol is as follows:
Ti (O
X3C
Y3H
Z3)
M3, m3 is the integer of 1-4, x3 is the integer of 1-2,12 〉=y3 〉=1 and be integer;
When x3=1, z3=2y3;
When x3=2, z3=2y3+1;
Z is an integer;
Said solvent is low boiling point solvents such as methyl alcohol, ethanol, acetone or acetyl-pyrrole alkane ketone, the perhaps polyol component in the reaction system, and the consumption of solvent is 192x-2.2 * 10
5X g, wherein x is the molar weight of titanium alkoxide;
Sequestrant is hydrochloric acid, acetic acid or citric acid etc., and its consumption is 1 * 10 of a used titanium alkoxide molar weight
-6-4 times of moles;
The consumption of water is 1 * 10 of a used titanium alkoxide molar weight
-6-4 times of moles;
Titanium series organic compound of the present invention and carboxylate/titanium series organic compound matrix material all can be used as polyester synthetic catalyzer, ultraviolet screener additive and modified-high polymer add material, method by blend or in-situ polymerization is incorporated in the high polymer system, give the polymer matrix function of shielding ultraviolet radiation, regulate its moulding processability; Carboxylate/titanium series organic compound matrix material also can be further through the synthetic polyester/titanium series organic compound matrix material that obtains of polycondensation.
Description of drawings
Fig. 1 is the SEM photo of BHET/ titanium series organic compound matrix material.
Fig. 2 is the TEM photo of the titanium series organic compound that centrifugation goes out from BHET/ titanium series organic compound matrix material.
Fig. 3 is the FTIR spectrum of the titanium series organic compound that centrifugation goes out from BHET/ titanium series organic compound matrix material.
Fig. 4 is the NMR collection of illustrative plates of the titanium series organic compound that centrifugation goes out from BHET/ titanium series organic compound matrix material.
Fig. 5 is the SEM of the titanium series organic compound that centrifugation goes out from carboxylate/titanium series organic compound matrix material.
Fig. 6 is the TEM photo of the titanium series organic compound that centrifugation goes out from carboxylate/titanium series organic compound matrix material.
Fig. 7 is the FTIR spectrum of the titanium series organic compound that centrifugation goes out from carboxylate/titanium series organic compound matrix material.
Fig. 8 is the WAXD collection of illustrative plates of the titanium series organic compound that centrifugation goes out from carboxylate/titanium series organic compound matrix material.
Embodiment
Embodiment 1
With 100g ethylene glycol, 20g distilled water and 1g sequestrant citric acid wiring solution-forming A;
To splash in the 200g ethylene glycol wiring solution-forming B under the stirring of 136g tetrabutyl titanate;
Under 40 ℃ of water-baths and stirring, solution A is splashed into solution B.
Add citric acid, the pH to 6 of regulation system refluxes and stirs 2h, obtains the ethylene glycol colloidal sol of the titanium of homogeneous transparent.
Ethylene glycol colloidal sol with above-mentioned 500g titanium, in terephthalic acid 498 grams (3 moles) and the 72 gram ethylene glycol, in temperature of reaction is 250 ℃, reaction pressure is a back flow reaction under the 0.4Mpa, collect distilled liquid in the esterification reaction process, when the mole number of wherein water be terephthalic acid 180% the time termination reaction, obtain ethylene glycol terephthalate (BHET)/titanium series organic compound matrix material.This matrix material is dissolved with 1: 1 (weight) phenol-tetrachloroethane, and centrifugation obtains titanium series organic compound.The SEM photo of matrix material is seen Fig. 1, the TEM photo of the titanium series organic compound that centrifugation goes out from BHET/ titanium series organic compound matrix material is seen Fig. 2, the FTIR spectrum of the titanium series organic compound that centrifugation goes out from BHET/ titanium series organic compound matrix material is seen Fig. 3, and the NMR collection of illustrative plates of the titanium series organic compound that centrifugation goes out from BHET/ titanium series organic compound matrix material is seen Fig. 4.
Embodiment 2
With 80g acetone, 20g distilled water and 1g sequestrant acetic acid wiring solution-forming A;
The 136g tetrabutyl titanate is under agitation splashed in the 200g acetone wiring solution-forming B;
Under 40 ℃ of water-baths and stirring, the 101g solution A is splashed into solution B.
Adopt about the pH to 6 of acetic acid regulation system, reflux and stir 2h, obtain the ethylene glycol colloidal sol of the titanium of homogeneous transparent.
Above-mentioned 200g titanium colloidal sol is joined 0.4mol terephthalic acid, 0.4mol hexanodioic acid, 0.36mol hexylene glycol, 0.3mol neopentyl glycol and 0.2mol 2, in the reaction system of 2-dimethylol propionic acid, in temperature of reaction is back flow reaction under 210 ℃, 0.1Mpa pressure, collect distilled liquid in the esterification reaction process, when the mole number of wherein water is 1.3mol, termination reaction obtains carboxylate/titanium series organic compound matrix material.With this matrix material acetone diluted, centrifugation obtains titanium series organic compound.The SEM and the TEM photo of the titanium series organic compound that centrifugation goes out from carboxylate/titanium series organic compound matrix material are seen Fig. 5 and Fig. 6, the FTIR spectrum of the titanium series organic compound that centrifugation goes out from carboxylate/titanium series organic compound matrix material is seen Fig. 7, and the WAXD collection of illustrative plates of the titanium series organic compound that centrifugation goes out from carboxylate/titanium series organic compound matrix material is seen Fig. 8.
Embodiment 3
BHET/ titanium series organic compound matrix material with 1 gram, 2 grams, 3 embodiment 1 that restrain adds in terephthalic acid 498 grams (3 moles) and 279 gram (4.5 moles) ethylene glycol respectively, in temperature of reaction is 250 ℃, reaction pressure is a back flow reaction under the 0.4Mpa, collect distilled liquid in the esterification reaction process, when the mole number of wherein water be terephthalic acid 180% the time, vacuumize, carry out polycondensation, discharging when reaching certain power of agitator.The physical and chemical index of prepared PET resin is as shown in table 1.
Table 1 is made the physical and chemical index of catalyzer synthetic PET resin with BHET/ titanium series organic compound matrix material.
| Physicochemical property | Carboxylate/titanium series organic compound matrix material/g | ||
| 1 | 2 | 3 | |
| High vacuum polycondensation time/min colourity (L) colourity (b) colourity (a) DEG/% holds carboxyl/molkg
-1Relative viscosity/ |
81 74.59 8.42 -1.74 4.10 5.8 0.642 | 70 72.54 11.16 -2.41 3.77 20.4 0.638 | 66 72.24 15.82 -3.53 3.41 19.9 0.640 |
Carboxylate/titanium series organic compound matrix material can be used as the catalyzer of synthetic PET, from table 1 the used as can be seen catalysis time of data shorter, the synthetic PET hue is good, every index all reaches requirement.
Embodiment 4
Will be from embodiment 2 isolated titanium series organic compound and PET resin 300 ℃ through the twin screw extruder melt blending, making titanium content is the PET base compound resin of 0.5wt%, this resin is made the film of different draw ratio 105 ℃ of two-way stretches.The two-way stretch performance of PET and compound resin thereof is more as shown in table 2.
The two-way stretch different multiples performance of table 2PET and compound resin thereof relatively
| Sample | The two-way stretch performance | |||
| 1.0×1.0 | 3.7×3.7 | 4.0×4.0 | 4.5×4.5 | |
| PET PET/ titanium series organic compound compound resin | + + | + + | - + | - + |
+: can the two-way stretch film forming;-: can not the two-way stretch film forming;
By table 2 as seen, behind the introducing titanium series organic compound, the moulding processability of PET resin is improved,
The ultraviolet-shielding type rate of the BOPET film that its two-way stretch is 1.0 * 1.0 times can reach 99.9%.
Claims (9)
1. titanium series organic compound material is characterized in that general structure is as follows:
Wherein:
R
1Be C
xH
yO
z, x=2～18, y=2～36 and z=0～1 and be integer;
R
2Be C
xH
y, x=2～18, y=2～36 and be integer;
R
3Be C
xH
yO
z, x=0～2000 and be integer, y=1～4000 and be integer, z=1～800 and be integer.
2. the method for preparing the described titanium series organic compound of claim 1, its feature like this, comprise the steps: titanium colloidal sol is mixed with polyvalent alcohol matter, add di-carboxylic acid then, backflow esterification under 100-300 ℃ of temperature and the 0-0.6Mpa pressure, collect distilled liquid in the esterification reaction process, when the mole number of distillate termination reaction when being 0.20-4.0 times of used di-carboxylic acid class material, obtain carboxylate/titanium series organic compound matrix material, with the direct centrifugation of this matrix material, or, can obtain titanium series organic compound with centrifugation after the dissolution with solvents.
3. method according to claim 2 is characterized in that, proportioning raw materials in the reaction system:
0.01≤D≤0.5; D=di-carboxylic acid/polyvalent alcohol, mol ratio;
The amount of used titanium colloidal sol is that wherein the amount of titanium component is 0.1～50% of a di-carboxylic acid molar weight.
4. method according to claim 2 is characterized in that the chemical structure of general formula of said polyvalent alcohol is as follows: HO-C
X1H
Y1O
Z1-OH;
Wherein:
X1=2～18, y1=2～36 and z1=0～1 and be integer.
5. method according to claim 4 is characterized in that, polyvalent alcohol is an ethylene glycol, 1, ammediol, 1,4-butyleneglycol, neopentyl glycol, TriMethylolPropane(TMP), 2, one or more in 2-dimethylol propionic acid or the hexylene glycol.
6. method according to claim 2 is characterized in that, the chemical structure of general formula of said di-carboxylic acid is as follows:
R
5OC-C
x2H
y2-COR
5；
X2=2～18, y=2～36 and be integer;
R
5Be Cl, Br or C
mH
nO, m=0～18 wherein, n=1～36, and be integer.
7. method according to claim 6, it is characterized in that di-carboxylic acid is a terephthalic acid, m-phthalic acid, phthalic acid, to naphthalic acid, between naphthalic acid, adjacent naphthalic acid, dimethyl terephthalate (DMT), diethyl terephthalate, dimethyl isophthalate, dimethyl isophthalate, dimethyl phthalate, diethyl phthalate, to naphthalene diformic acid dimethyl ester, to the naphthalic acid diethyl ester, between naphthalene diformic acid dimethyl ester, between the naphthalic acid diethyl ester, adjacent naphthalene diformic acid dimethyl ester, adjacent naphthalic acid diethyl ester, in m-phthalic acid or the hexanodioic acid one or more.
8. method according to claim 2 is characterized in that, the preparation method of said titanium colloidal sol is as follows:
Solvent, water and sequestrant wiring solution-forming A with cumulative volume 20%-60%;
The titanium alkoxide is under agitation splashed in the solvent of surplus wiring solution-forming B;
Solution A is splashed into solution B, and the pH of regulation system refluxes and stirred 0.5～5 hour at 4-6.5, obtains the titanium colloidal sol of homogeneous transparent; The content of titanium is 0.03-25wt% in the obtained titanium colloidal sol.
Said titanium alkoxide chemistry skeleton symbol is as follows:
Ti (O
X3C
Y3H
Z3)
M3, m3 is the integer of 1-4, x3 is the integer of 1-2,12 〉=y3 〉=1 and be integer;
When x3=1, z3=2y3; When x3=2, z3=2y3+1, z3 are integer;
Said solvent is low boiling point solvents such as methyl alcohol, ethanol, acetone or acetyl-pyrrole alkane ketone, the perhaps polyol component in the reaction system, and the consumption of solvent is 192x-2.2 * 10
5X g, wherein x is the molar weight of titanium alkoxide;
Sequestrant is hydrochloric acid, acetic acid or citric acid etc., and its consumption is 1 * 10 of a used titanium alkoxide molar weight
-6-4 times of moles;
The consumption of water is 1 * 10 of a used titanium alkoxide molar weight
-6-4 times of moles.
9. the application of titanium series organic compound material according to claim 1, it is characterized in that, add material as polyester synthetic catalyzer, ultraviolet screener additive or modified-high polymer, carboxylate/titanium series organic compound matrix material is further through the synthetic polyester/titanium series organic compound matrix material that obtains of polycondensation.
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|---|---|---|---|
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ID=39918984
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| CN107141462A (en) * | 2017-06-06 | 2017-09-08 | 北京化工大学 | A kind of preparation method and application of polyester Titanium series catalyst |
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2008
- 2008-03-03 CN CNA2008100341481A patent/CN101235049A/en active Pending
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| CN103088460A (en) * | 2013-01-04 | 2013-05-08 | 东华大学 | High-strength industrial polyester fiber and preparation method thereof |
| CN103088460B (en) * | 2013-01-04 | 2016-01-13 | 东华大学 | A kind of High-strength industrial polyester fiber and preparation method thereof |
| CN107141462A (en) * | 2017-06-06 | 2017-09-08 | 北京化工大学 | A kind of preparation method and application of polyester Titanium series catalyst |
| CN111019101A (en) * | 2019-12-31 | 2020-04-17 | 绍兴惠群新材料科技有限公司 | Method for preparing PBT copolyester |
| CN111019102A (en) * | 2019-12-31 | 2020-04-17 | 上海慧翌新材料科技有限公司 | Method for preparing titanium-based polyester by DMT method |
| CN111019106A (en) * | 2019-12-31 | 2020-04-17 | 上海慧翌新材料科技有限公司 | Titanium-based phosphorus-containing copolyester and preparation method thereof |
| CN111019102B (en) * | 2019-12-31 | 2022-04-15 | 上海慧翌新材料科技有限公司 | Method for preparing titanium-based polyester by DMT method |
| CN111019106B (en) * | 2019-12-31 | 2022-04-15 | 上海慧翌新材料科技有限公司 | Titanium-based phosphorus-containing copolyester and preparation method thereof |
| CN113881027A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Titanium polyester catalyst and preparation method and application thereof |
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