CN103772671A - Polymerization method of polyester resin - Google Patents
Polymerization method of polyester resin Download PDFInfo
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- CN103772671A CN103772671A CN201210412544.XA CN201210412544A CN103772671A CN 103772671 A CN103772671 A CN 103772671A CN 201210412544 A CN201210412544 A CN 201210412544A CN 103772671 A CN103772671 A CN 103772671A
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Abstract
The invention relates to a polymerization method of polyester resin, which mainly solves the problems that solid phase polymerization of a titanium catalyzed and synthetized bottle grade polyester chip after a bottle grade is relatively slow and the content of acetaldehyde is high in the existing production process. The method comprises the steps that dicarboxylic acid and alkylene glycol serve as raw materials; esterification reaction is performed in the presence of a titanium catalyst; condensation polymerization is performed under a vacuum condition; a polyester product is obtained; and before the condensation polymerization step, at least one metal compound G selected from IIA, IB, IIB, VIIB and VIII in a periodic table of elements serves as a promoter and is added to a reaction system. With the adoption of the technical scheme, the problems are solved better, so that the method can be used in industrial production of polyester.
Description
Technical field
The present invention relates to a kind of polymerization process of vibrin.
Background technology
In industrial production research at present and applied research, more than 90% PET in the whole world produces and adopts antimony-based catalyst (comprising antimonous oxide, antimony acetate and antimony glycol etc.).The shortcoming of this catalyzer is: antimony-based catalyst contains heavy metal to environment; Polymer belt grey.Along with the enhancing of people's environmental consciousness, will be more and more stricter to the restriction of antimony.The Titanium series catalyst of nontoxic heavy metal free is the kind polyester catalyzer that current research is maximum.Titanium series polyester catalyst has high reactivity, but the poor and goods yellowing of the polyester existence and stability that titanium series polyester catalyst makes, muddy problem, thereby never used on a large scale.
More and more pay close attention in the whole world under the background of environment for human survival, the overall development trend of polyester catalyst is to environmental protection, efficient, low toxicity and nontoxic future development, the production and selling of green product is by the trend that is following polyester development, can the developed country using European Union as representative reach green product standard more and more as the condition coming into the market, through the development of more than 10 years, European Union's eco-label (Eco-label) is approved by the human consumer of European Union gradually, sticks on the also raising gradually of pouplarity of Ecolabelling commodity.
Titanium series polyester catalyst is because its activity is high, do not contain heavy metal, there is not problem of environmental pollution, catalyst activity is high, can Reaction time shorten, improve unit production capacity, adopt the increase of polyester transparent degree, the gray scale that titanium series polyester catalyst is produced to decline, in polyester, residual amount of metal is only 1/tens of antimony simultaneously, can be used for producing high-grade film, spinning and packing bottle.
Along with the raising of socioeconomic development and people's living standard, PET Bottle Chip has obtained application more and more widely in the fields such as food, medicine, beverage.Wherein the wrapping polyester bottle slice of food-drink accounts for 80% of total amount.With respect to antimony-based catalyst, the Titanium series catalyst widespread adoption of nontoxic heavy metal free is produced and is seemed very necessary in bottle sheet.On the other hand, the heavy metal catalyst acetaldehyde in bottle sheet can affect mouthfeel and the quality of food-drink, and the acetaldehyde of therefore controlling well in bottle sheet is very crucial.
CN1328072 and CN1327985 disclose the diatomic alcohol compounds that generates a kind of granular titanium using titanic acid ester and glycol reaction as polyester catalyst, this granular polyester catalyst likely in the industrial production of polyester band serve application problem, and in patent, do not report for work and adopt the form and aspect of the polyester that makes of this catalyzer.
CN1962722A and CN1962723A have solved the poor problem of light stability that has titanium in conventional art;
CN1798798 discloses the polyester of a kind of titaniferous, magnesium, three kinds of elements of phosphorus, has solved the problem of titanium polyester poor heat stability;
CN101121778A has solved in conventional art and has existed the titanium and the dibastic alcohol compound catalyzer that make poorly soluble in ethylene glycol, the problems such as the PET hue making is partially yellow, but in patent, all do not relate to the relevant report of the polyester solid phase polymerization that this catalyzer makes.
CN1954012 and WO2008008836 disclose and in polymerization system, have added an alkali metal salt and alkaline earth salt, can improve the solid phase polycondensation speed of polyester, but relevant report is not made in the impact that the addition sequence in production of polyester increases solid phase polycondensation viscosity on an alkali metal salt and alkaline earth salt.
CN200880022488.0 discloses a kind of solid phase polycondensation method of Hypophosporous Acid, 50 compound with the polyester of raising organic titanate catalysis that add, wherein polyester demonstrates the generation of low acetaldehyde in melt-processed, but in patent, does not relate to the relevant report of acetaldehyde after solid phase polycondensation.
Summary of the invention
Technical problem to be solved by this invention is the problem that polyester solid phase polymerization speed is slow, acetaldehyde is higher that in the past prepared by Titanium series catalyst, and a kind of polymerization process of new vibrin is provided.The method has that the polyester solid phase polymerization speed obtaining is fast, and acetaldehyde is lower, simultaneously the good advantage of form and aspect.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of polymerization process of vibrin, comprises the following steps:
A) take di-carboxylic acid and dibasic alcohol as raw material, it is 230～280 ℃ in temperature of reaction, reaction pressure is to carry out esterification under normal pressure～0.5MPa condition, obtain prepolymer, then be 250～320 ℃ in temperature of reaction, reaction pressure is to be less than under the vacuum condition of 150Pa, to carry out melt polycondensation reaction and obtain polyester product; The catalyzer using comprises that following raw material is in 0～200 ℃ of reaction reaction product of 0.5～10 hour:
(1) there is the titanium compound A of following general formula:
Ti(OR)
4
R is straight chain or the branched-alkyl that is selected from 1～10 carbon atom;
(2) be selected from the dibasic alcohol B with 2～10 carbon atoms;
(3) be selected from least one the metallic compound C of IA in the periodic table of elements;
(4) be selected from least one the aliphatics organic acid D in organic acid;
(5) be selected from least one the phosphate compound E in phosphorus compound;
(6) be selected from least one the metallic compound F in IIA in the periodic table of elements, IB, IIB, VIIB, VIII;
Wherein, the mol ratio of dibasic alcohol B and titanium compound A is 1～8: 1; The mol ratio of metallic compound C and titanium compound A is 0.1～10: 1; The mol ratio of aliphatics organic acid D and titanium compound A is 1～20: 1; The mol ratio of phosphate compound E and titanium compound A is >0～10: 1; The mol ratio of metallic compound F and titanium compound A is 0.1～20: 1;
Before polycondensation, add at least one the metallic compound G being selected from IIA in the periodic table of elements, IB, IIB, VIIB, VIII as promotor, the weight that the consumption of metallic compound G obtains polyester product based on melt polycondensation reaction is 1～100ppm;
B) polyester product melt phase polycondensation being obtained, after pre-crystallized processing, is 200～250 ℃ in temperature of reaction, and reaction pressure is to be less than under the condition of 100Pa to carry out solid state polymerization to obtain the high viscosity polyester of (limiting viscosity dl/g is greater than 0.9).
In technique scheme, titanium compound A is selected from least one compound in metatitanic acid tetramethyl ester, tetraethyl titanate, the own ester of metatitanic acid tetraethyl-, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate, the different monooctyl ester of metatitanic acid four.Dibasic alcohol B is selected from the one in 1,2-PD, 1,3-PD, BDO, ethylene glycol, Diethylene Glycol.Metallic compound C is selected from least one in the compound of the elements such as the lithium, sodium, potassium of IA family in the periodic table of elements.Aliphatics organic acid D is selected from least one in lactic acid, citric acid, oxysuccinic acid, tartrate, oxalic acid.Phosphate compound E is at least one phosphate compound being selected from methyl-phosphoric acid, monoethyl-phosphate, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or triphenylphosphate.Metallic compound F and metallic compound G are at least one metallic compounds being selected from zinc, manganese, magnesium, calcium or cobalt element, comprise the organic salt of these elements and the hydrate of salt, as magnesium acetate, zinc acetate, Cobaltous diacetate etc.
In technique scheme, di-carboxylic acid is selected from least one in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid, preferably terephthalic acid; Dibasic alcohol is selected from ethylene glycol, 1,3-PD, BDO, 1, at least one in 6-hexylene glycol and 1,4 cyclohexane dimethanol, preferably ethylene glycol.The mol ratio of dibasic alcohol B and titanium compound A is preferably 1～4: 1; The mol ratio of metallic compound C and titanium compound A is preferably 0.1～6: 1; The mol ratio of aliphatics organic acid D and titanium compound A is preferably 1～15: 1; The mol ratio of phosphoric acid ester phosphorus compound E and titanium compound A is preferably >0～6: 1; The mol ratio of metallic compound F and titanium compound (A) is preferably 0.1～10: 1; The weight preferable range that the consumption of the metallic compound F adding obtains polyester product based on melt polycondensation reaction is 1～50ppm.
In technique scheme, the polyester product of the melt phase polycondensation for solid state polymerization obtaining is solid-state.The temperature of reaction preferable range of preparing polyester catalyst is 10～180 ℃, and reaction times preferable range is 2～6 hours.Obtain the weight of polyester product based on melt polycondensation reaction, the addition of catalyzer is take titanium atom preferable range as 1～20ppm.Catalyzer is homogeneous phase liquid catalyst, can dissolve each other with ethylene glycol.
The preparation method of titanium series polyester catalyst of the present invention is as follows:
Add at least one metallic compound, organic acid and the phosphorus combination reaction that in the dibasic alcohol of aequum, at least one metallic compound that is selected from IA in the periodic table of elements, the periodic table of elements, are selected from IIA, IB, IIB, VIIB or VIII to obtain homogeneous phase liquid titanium polyester catalyzer titanium compound.
The preparation method of polyester is as follows:
Can adopt known preparation process of polyester, the first step is carried out esterification by di-carboxylic acid and dibasic alcohol, obtains prepolymer, and temperature of reaction is 230～280 ℃, and reaction pressure is normal pressure～0.5MPa.Second step carries out polycondensation under high vacuum, 250～320 ℃ of temperature of reaction, and reaction pressure is for being less than 150Pa.Catalyzer can select before esterification or esterification joins in reaction system after finishing.After finishing, reaction carries out pelletizing preservation.
Before esterification or esterification finish finishing reaction and start front metallic compound G to be joined in system, addition be 1～100ppm(based on melt polycondensation reaction obtain polyester product weight).
Solid state polymerization (SSP) method of polyester:
Polyester prepared by aforesaid method further carries out solid state polymerization and improves viscosity.Carrying out before solid state polymerization, should first carry out pre-crystallized processing to polyester.Polyester granulate prepared by above-mentioned preparation process of polyester, is placed in 80～130 ℃, preferably under the vacuum environment of 90～120 ℃, heats and is dried for 1 minute～3 hours.After dry end, under atmosphere of inert gases or vacuum environment, by temperature increase to 100～180 ℃, preferably 140～170 ℃ are carried out pre-crystallizedly, and crystallization time is 1 hour～10 hours, preferably 3 hours～7 hours.
After pre-crystallized end, particle being sent into thermal oil reaction unit, is to be less than under the vacuum of 100Pa particle to carry out solid-phase polymerization in nitrogen protection state, reaction pressure.Temperature of reaction is 200～250 ℃, and preferably 210～230 ℃, equipment was warming up to set(ting)value in 1 hour.Reaction times is 1 hour～20 hours, preferably 3 hours～10 hours.
In the present invention, limiting viscosity and the form and aspect etc. of polyester are tested by the following method:
(1) limiting viscosity: the mixed liquid of phenol tetrachloroethane is made solvent, uses determination of ubbelohde viscometer at the temperature of 25 ℃.
(2) form and aspect: pellet sample is measured its Hunter L value (brightness), a value (yellow-blue form and aspect) and b value (red-green form and aspect) with the color-view automatic colour difference meter of BYK Gardner company 135 ℃ of processing after 1 hour.Wherein, L value is higher, and brightness is larger; B value height polyester slice is partially yellow.For the present invention, wish to pursue high L value, low b value.
(3) acetaldehyde (AA): accurate weighing 0.5g packs in head space bottle after the polyester sample of solid phase polycondensation is pulverized, with air in nitrogen replacement bottle sealing.Set 150 ℃ of head-space sampler furnace temperature, starting time 60 minutes.The acetaldehyde of sample uses gas chromatograph (GC7890, Agilent) to carry out quantitative analysis by headspace sampling.
The present invention prepares polyester by employing Titanium series catalyst, and the polyester making is carried out to solid-phase polymerization.The discovery that the inventor is surprised, the polyester and the polyester that does not add metallic compound G that adopt the method to make contrast after solid state polymerization, solid state polymerization speed, acetaldehyde is lower, and there is not considerable change in form and aspect, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The preparation of catalyst A
In the reactor that agitator, condenser and thermometer are housed, add 12.4 grams of ethylene glycol (0.2 mole), in reactor, slowly splash into 28.4 grams of titanium isopropylates (0.1 mole), separate out white depositions, at 70 ℃, react 2 hours, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 ℃, obtain white powder material.
Dried white powder material is placed in to the reactor with agitator, condenser and thermometer, add 50 grams of ethylene glycol, the aqueous sodium hydroxide solution (0.2 mole) of 32 gram 25%, 73.2 grams of zinc acetates (0.4 mole), 18 grams of lactic acid (0.2 mole), 28 grams of trimethyl phosphite 99s (0.2 mole) react 2 hours under 150 ℃ of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyst A.
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and the catalyst A (amount of the polyester based on generating, the weight of titanium atom is 2.5ppm), the mixed slurry that is made into, join in polymeric kettle, carry out esterification, esterification temperature is 230～255 ℃, and pressure is 0.25MPa, discharges by rectifier unit the water that reaction generates.After finishing, esterification is down to normal pressure, add the amount of the polyester of zinc acetate 18ppm(based on generating), vacuumize and be decompressed to system pressure lower than 100Pa, simultaneous reactions temperature rises to 280 ℃ gradually, stopped reaction after system reaction reaches 150min, afterwards reaction product is extruded continuously to cooling, pelletizing with bar shaped from polymeric kettle bottom.
The solid state polymerization of polyester
The polyester granulate that liquid polycondensation is obtained is dried under vacuum environment, the condition of 100 ℃, temperature increase to 160 ℃ is carried out to pre-crystallized processing 6 hours after dry.The solid state polycondensation that particle after treatment is positioned in thermal oil reaction unit and carries out polyester under nitrogen protection state, 0.1kPa, the condition of 230 ℃, the reaction times is 10 hours.Cooling rear taking-up.
Test result is in table 1.
[embodiment 2]
Except the amount of promotor zinc acetate being changed into the amount of the polyester of 9ppm(based on generating), adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 3]
Except the amount of promotor zinc acetate being changed into the amount of the polyester of 36ppm(based on generating), adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 4]
Except promotor zinc acetate being replaced with to the amount of the polyester of magnesium acetate 18ppm(based on generating), adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 5]
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol, the catalyst A (amount of the polyester based on generating, the weight of titanium atom is 2.5ppm) and the amount of polyester of zinc acetate 18ppm(based on generating), the mixed slurry that is made into, join in polymeric kettle, carry out esterification, esterification temperature is 230～255 ℃, and pressure is 0.25MPa, discharges by rectifier unit the water that reaction generates.After esterification finishes, be down to normal pressure, vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 ℃ gradually, and stopped reaction after system reaction reaches 150min is extruded reaction product with bar shaped cooling, pelletizing afterwards continuously from polymeric kettle bottom.
Method is similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
[embodiment 6]
Except the amount of zinc acetate being changed into the amount of the polyester of 9ppm(based on generating), adopt to use the same method with embodiment 5 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 7]
The preparation of catalyst B
In the reactor that agitator, condenser and thermometer are housed, add 12.4 grams of ethylene glycol (0.2 mole), in reactor, slowly splash into 28.4 grams of titanium isopropylates (0.1 mole), separate out white depositions, at 70 ℃, react 2 hours, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 ℃, obtain white powder material.
Dried white powder material is placed in to the reactor with agitator, condenser and thermometer, add 50 grams of ethylene glycol, the potassium hydroxide aqueous solution (0.2 mole) of 44.8 gram 25%, 146.4 grams of zinc acetates (0.8 mole), 18 grams of lactic acid (0.2 mole), 28 grams of trimethyl phosphite 99s (0.2 mole) react 2 hours under 150 ℃ of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyst B.
Carry out the preparation of polyester and the solid-phase polymerization of polyester according to the method for embodiment 1.
Test result is in table 1.
[embodiment 8]
Except catalyst A (amount of the polyester based on generating, the weight of titanium atom is 2.5ppm) is changed into outside 5ppm, carry out the preparation of polyester and the solid-phase polymerization of polyester according to the method for embodiment 1.
Test result is in table 1.
[comparative example 1]
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and the catalyst A (amount of the polyester based on generating, the weight of titanium atom is 2.5ppm), the mixed slurry that is made into, join in polymeric kettle, carry out esterification, esterification temperature is 230～255 ℃, and pressure is 0.25MPa, discharges by rectifier unit the water that reaction generates.After esterification finishes, be down to normal pressure, vacuumize and be decompressed to system pressure lower than 130Pa, simultaneous reactions temperature rises to 280 ℃ gradually, and stopped reaction after system reaction reaches 150min is extruded reaction product with bar shaped cooling, pelletizing afterwards continuously from polymeric kettle bottom.
By method similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
[comparative example 2]
Except promotor zinc acetate being replaced with to the amount of the polyester of sodium-acetate 18ppm(based on generating), adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[comparative example 3]
The preparation of catalyzer C
In the reactor that agitator, condenser and thermometer are housed, add 12.4 grams of ethylene glycol (0.2 mole), in reactor, slowly splash into 28.4 grams of titanium isopropylates (0.1 mole), separate out white depositions, at 70 ℃, react 2 hours, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 ℃, obtain white powder material.
Dried white powder material is placed in to the reactor with agitator, condenser and thermometer, add 50 grams of ethylene glycol, the aqueous sodium hydroxide solution (0.2 mole) of 32 gram 25%, four 21.4 grams, water acetic acid magnesium (0.1 mole), 18 grams of lactic acid (0.2 mole), 28 grams of trimethyl phosphite 99s (0.2 mole) react 2 hours under 150 ℃ of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyzer C.
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and the catalyst A (amount of the polyester based on generating, the weight of titanium atom is 2.5ppm), the mixed slurry that is made into, join in polymeric kettle, carry out esterification, esterification temperature is 230～255 ℃, and pressure is 0.25MPa, discharges by rectifier unit the water that reaction generates.After esterification finishes, be down to normal pressure, vacuumize and be decompressed to system pressure lower than 100Pa, simultaneous reactions temperature rises to 280 ℃ gradually, and stopped reaction after system reaction reaches 150min is extruded reaction product with bar shaped cooling, pelletizing afterwards continuously from polymeric kettle bottom.
Adopt to use the same method with embodiment 1 polyester granulate is carried out to solid state polymerization.
Test result is in table 1.
[comparative example 4]
Adopt antimony glycol as catalyzer (amount of the polyester based on generating, the weight of antimony atoms is 180ppm).Adopt to use the same method with comparative example 3 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
Table 1
Claims (10)
1. a polymerization process for vibrin, comprises the following steps:
A) take di-carboxylic acid and dibasic alcohol as raw material, it is 230～280 ℃ in temperature of reaction, reaction pressure is to carry out esterification under normal pressure～0.5MPa condition, obtain prepolymer, then be 250～320 ℃ in temperature of reaction, reaction pressure is to be less than under the vacuum condition of 150Pa, to carry out melt polycondensation reaction and obtain polyester product; The catalyzer using comprises that following raw material is in 0～200 ℃ of reaction reaction product of 0.5～10 hour:
(1) there is the titanium compound A of following general formula:
Ti(OR)
4
R is straight chain or the branched-alkyl that is selected from 1～10 carbon atom;
(2) be selected from the dibasic alcohol B with 2～10 carbon atoms;
(3) be selected from least one the metallic compound C of IA in the periodic table of elements;
(4) be selected from least one the aliphatics organic acid D in organic acid;
(5) be selected from least one the phosphate compound E in phosphorus compound;
(6) be selected from least one the metallic compound F in IIA in the periodic table of elements, IB, IIB, VIIB, VIII;
Wherein, the mol ratio of dibasic alcohol B and titanium compound A is 1～8: 1; The mol ratio of metallic compound C and titanium compound A is 0.1～10: 1; The mol ratio of aliphatics organic acid D and titanium compound A is 1～20: 1; The mol ratio of phosphate compound E and titanium compound A is >0～10: 1; The mol ratio of metallic compound F and titanium compound A is 0.1～20: 1;
Before polycondensation, add at least one the metallic compound G being selected from IIA in the periodic table of elements, IB, IIB, VIIB, VIII as promotor, the weight that the consumption of metallic compound G obtains polyester product based on melt polycondensation reaction is 1～100ppm;
B) polyester product melt phase polycondensation being obtained, after pre-crystallized processing, is 200～250 ℃ in temperature of reaction, and reaction pressure is to be less than under the condition of 100Pa to carry out solid state polymerization is greater than 0.9 deciliter/gram polyester to obtain limiting viscosity.
2. the polymerization process of vibrin according to claim 1, is characterized in that di-carboxylic acid is selected from least one in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid; Dibasic alcohol is selected from ethylene glycol, 1,3-PD, BDO, 1, at least one in 6-hexylene glycol and 1,4 cyclohexane dimethanol.
3. the polymerization process of vibrin according to claim 1, is characterized in that titanium compound A is selected from least one in metatitanic acid tetramethyl ester, tetraethyl titanate, the own ester of metatitanic acid tetraethyl-, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate, the different monooctyl ester of metatitanic acid four.
4. the polymerization process of vibrin according to claim 1, is characterized in that dibasic alcohol B is selected from least one in 1,2-PD, 1,3-PD, BDO, ethylene glycol, Diethylene Glycol.
5. the polymerization process of vibrin according to claim 1, is characterized in that metallic compound C is selected from least one in lithium, sodium or potassium compound.
6. the polymerization process of vibrin according to claim 1, is characterized in that aliphatics organic acid D is selected from least one in lactic acid, citric acid, oxysuccinic acid, tartrate or oxalic acid.
7. the polymerization process of vibrin according to claim 1, is characterized in that phosphate compound E is selected from least one in methyl-phosphoric acid, monoethyl-phosphate, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or triphenylphosphate.
8. the polymerization process of vibrin according to claim 1, is characterized in that metallic compound F is selected from least one in zinc, manganese, magnesium, calcium or cobalt compound.
9. the polymerization process of vibrin according to claim 1, is characterized in that metallic compound G is selected from least one in zinc, manganese, magnesium, calcium or cobalt compound.
10. the polymerization process of vibrin according to claim 1, is characterized in that obtaining based on melt polycondensation reaction the weight of polyester product, and the addition of catalyzer is counted 1～20ppm with titanium atom.
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| CN111087594A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Synthetic method of uvioresistant titanium polyester |
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Application publication date: 20140507 |