CN105482084A - Polyester containing unsaturated double bond and preparation method thereof - Google Patents
Polyester containing unsaturated double bond and preparation method thereof Download PDFInfo
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- CN105482084A CN105482084A CN201511016167.8A CN201511016167A CN105482084A CN 105482084 A CN105482084 A CN 105482084A CN 201511016167 A CN201511016167 A CN 201511016167A CN 105482084 A CN105482084 A CN 105482084A
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- 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
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- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- 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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- Macromonomer-Based Addition Polymer (AREA)
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Abstract
The invention relates to polyester containing an unsaturated double bond and a preparation method thereof. The polyester is prepared from terephthalic acid, unsaturated dicarboxylic acid and ethylene glycol by means of esterification and condensation polymerization under the effects of catalysis of the mixture of ethylene glycol magnesium and ethylene glycol antimony; granulating to obtain polyester chips. In the polyester chips, the content of terminal carboxyl group is less than 20mol/t, the mass percentage content of oligomer is less than 1.0 percent, and the mass percentage content of diethylene glycol is less than 1.0 percent. According to the preparation method, ethylene glycol magnesium is relatively mild, and is also a thermal degradation catalyst with small thermal degradation coefficient, and can cause few side effects in the reacting process, so that generation of terminal carboxyl group and oligomer in the processing process can be reduced. The oligomer is reduced in the polymerizing process, and thermal degradation is reduced in the processing process, so that impurities in the polyester are greatly reduced, the quantity of a nucleating agent in the polyester is reduced at the same, the probability of homogeneous nucleation is increased on the basis of reducing heterogeneous nucleation, and growth of grain size and crystal completeness optimization in polyester industrial yarn fibers can be benefited.
Description
Technical field
The invention belongs to polyester preparing technical field, relate to a kind of containing unsaturated double-bond polyester and preparation method thereof, particularly a kind ofly adopt polyester of the mixture of ethylene glycol magnesium and antimony glycol and preparation method thereof containing unsaturated double-bond and polycondensation catalyst.
Background technology
Polyethylene terephthalate (PET) is a kind of polymkeric substance of excellent property, PET is high with its modulus, intensity is high, well-pressed, conformality good, pure health, barrier property are good, be widely used in the fields such as fiber, bottle packaging, film and sheet material, output cumulative year after year, position in industry significantly promotes.
Polyester containing unsaturated double-bond is unsaturated polyester, it refers to the chain macromolecule compound formed by saturated/unsaturated dibasic alcohol and saturated/unsaturated dibasic acid polycondensation, simultaneously containing ester bond and unsaturated double-bond in molecular backbone chain, therefore there is the characteristic of ester bond and unsaturated double-bond.Because it is linear macromolecule structure, therefore also referred to as linear unsaturated polyester.Unsaturated polyester has good formability and manufacturability because of it, and a series of advantages such as good mechanical property, erosion resistance and electric insulating quality, in all respects of productive life, have a wide range of applications.Unsaturated polyester is be applied to resin aspect more, the aspect such as main ships and light boats, vehicle part, sports equipment and polyester coating, technology for producing artificial jadeware product, artificial marble.Unsaturated double-bond is introduced at trevira, and control effectively, safely its be cross-linked, mechanical property to trevira, resistance toheat, chemical resistance, flame retardant properties there are is the raising compared with amplitude, how to have used unsaturated double-bond to be problem very important in trevira production technique.
End carboxyl, oligopolymer, glycol ether (DEG) content are the important quality index of polyester slice, and wherein oligopolymer, glycol ether are all oligopolymer, and they not only reflect the quality of production status, also can have influence on the quality product of spinning processing.Therefore, the end carboxyl in minimizing polyester slice, oligopolymer, diethylene glycol content just become and improve the very important link of polyester product quality.Control the content of three in polyester slice extremely important to the quality promoting trevira.The thermostability impact of end carboxyl on polymkeric substance is very large.Control polyester content of carboxyl end group is only had to stablize aborning, the homogeneity of its relative molecular mass distribution of control that could be stable.The content of glycol ether in polyester slice is a very important quality index in production of polyester.Because it directly has influence on the fusing point of polyester slice, the fusing point of polyester slice sharply can decline with the increase of the wherein content of DEG, so it not only reflects the quality of production status, directly has influence on the quality of post-treatment-spinning technique and silk.Oligopolymer in polyester refers to that the oligomer that the polymerization degree is less than 10 is divided into linear oligomerization thing and cyclic oligomer, wherein with ring-type aggressiveness, particularly cyclic trimer is in the majority, oligopolymer is mainly concerned with heterogeneous nucleation, spinning processing etc., causes certain detrimentally affect to the performance of polyester and the processing of rear road.
Summary of the invention
The object of this invention is to provide a kind of containing unsaturated double-bond polyester and preparation method thereof, is a kind ofly adopt polyester of the mixture of ethylene glycol magnesium and antimony glycol and preparation method thereof containing unsaturated double-bond and polycondensation catalyst.The present invention adopts the mixture of ethylene glycol magnesium and antimony glycol to be polycondensation catalyst, importantly thermal destruction coefficient is very little, thermal destruction is reduced to minimum, the impact that minimizing end carboxyl, oligopolymer, diethylene glycol content are processed Direct-spinning of PET Fiber, also ensure that the stability of unsaturated double-bond in polyester production process simultaneously.
One of the present invention containing unsaturated double-bond polyester, for the polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol of terephthalic acid, unsaturated dibasic acid and ethylene glycol obtains, then obtains polyester slice through pelletizing;
Described containing in unsaturated double-bond polyester slice, content of carboxyl end group is less than 20mol/t, and oligopolymer mass percentage content is less than 1.0%, and the mass percentage content of glycol ether is less than 1.0%; Described containing average containing 1 ~ 6 unsaturated double-bond provided by unsaturated dibasic acid molecule in unsaturated double-bond polyester macromolecular chain.
The molecular formula of described ethylene glycol magnesium is Mg (OCH
2cH
2oH)
2.
Unsaturated polyester is for saturated polyester, and the unsaturated link(age) containing non-aromatic in its molecular structure, unsaturated polyester ester molecule is generally long chain type molecular structure.Crosslinking reaction can be there is between the long chain molecule of unsaturated polyester and form baroque huge network molecule.The structure of network molecule is probably divided three classes: uniform continuous net-shaped structure; Uneven continuous net-shaped structure, is namely interconnected reticulated structure larger for density by the chain molecule that density is less; Discontinuous reticulated structure, highdensity continuous net-shaped structure disperses is in the middle of the component of non-bonding.After common unsaturated polyester generation crosslinking reaction, to generate uneven continuous net-shaped structure.The raising that after unsaturated polyester cross-linking, its mechanical property, resistance toheat, chemical resistance, flame retardant properties will have compared with amplitude.Selecting crosslinked is after prepared by fiber, and the mode caused by UV-light is carried out, and ensure that the double bond of polyester stablizing in the course of processing.
In polyester, the generation of end carboxyl is mainly in esterification and polycondensation phase, and the main side reaction in polycondensation process is thermal destruction, increases with response intensity, and thermal destruction is accelerated, and degraded causes PET conglutination to decline, and carboxyl end group value raises.Content of carboxyl end group is high, the poor heat stability of vibrin, and end carboxyl can carry out acidolysis reaction to ester group, can accelerate the hydrolysis reaction of ester group, and the electrical insulation capabilities such as the volume resistance of polyester can be made to reduce simultaneously.Polyester and carboxylate salt react the carboxylate salt of the polyester macromolecule chain generated, and consist of nucleus, make polyester accelerate heterogeneous nucleation.Glycol ether (DEG) directly has influence on the fusing point of polyester slice, the fusing point of polyester slice sharply can decline with the increase of the wherein content of DEG, so it not only reflects the quality of production status, also directly have influence on the quality of post-treatment-spinning technique and silk.Glycol ether is the ehter bond being very easy to oxidation, easily produces degraded when being heated.In the synthesis and the course of processing of polyester, the generation of oligopolymer main with PET thermal destruction and thermooxidative degradation closely bound up, oligopolymer is mainly concerned with heterogeneous nucleation, spinning processing etc., processes cause certain detrimentally affect to the performance of polyester and rear road.
One as above is containing unsaturated double-bond polyester, and the described number-average molecular weight containing unsaturated double-bond polyester is 15000 ~ 22000.
One as above is containing unsaturated double-bond polyester, and in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1.
Present invention also offers a kind of preparation method containing unsaturated double-bond polyester, for the polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol of terephthalic acid, unsaturated dibasic acid and ethylene glycol obtains polyester, then obtain polyester slice through pelletizing.
As above containing a preparation method for unsaturated double-bond polyester, specifically comprise the following steps:
(1) preparation of catalyst glycol magnesium:
In single-cell, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 6 ~ 10V, cathode current density is 150 ~ 200mA, electrolysis 10 ~ 12 hours when 50 ~ 60 DEG C, and electrolysis terminates rear taking-up electrode, obtains white suspension liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation:
Described esterification:
Adopt terephthalic acid, unsaturated dibasic acid and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure ~ 0.3MPa, and temperature is at 250 ~ 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, catalyzer, stablizer and ultraviolet initiator is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, and the reaction times is 30 ~ 50 minutes; Described catalyzer is the mixture of ethylene glycol magnesium and antimony glycol;
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and temperature of reaction controls at 275 ~ 280 DEG C, 50 ~ 90 minutes reaction times;
Obtained polyester, obtains polyester slice through pelletizing;
As above containing a preparation method for unsaturated double-bond polyester, the mol ratio of described ethylene glycol and described terephthalic acid is 1.2 ~ 2.0:1.
As above containing a preparation method for unsaturated double-bond polyester, in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1; Described catalyst levels is 0.01% ~ 0.05% of described terephthalic acid quality.Adopt ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium belongs to a comparatively gentle class, its thermal destruction coefficient is very little, the side reaction caused in reaction process is less, decrease the generation of end carboxyl and oligopolymer in the course of processing, also ensure that the stability of unsaturated double-bond in polyester production process simultaneously.
As above containing a preparation method for unsaturated double-bond polyester, described stablizer is selected from the one in triphenylphosphate, trimethyl phosphite 99 and trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.05% of described terephthalic acid weight.Stablizer is mainly based on phosphoric acid ester, and Main Function is the free radical of catching reaction generation in the course of the polymerization process, reduces side reaction, also protects unsaturated double-bond simultaneously.
As above containing a preparation method for unsaturated double-bond polyester, described unsaturated dibasic acid and terephthalic acid mol ratio are 1 ~ 5:100.
As above containing a preparation method for unsaturated double-bond heat-resistance polyester, described unsaturated dibasic acid is the one in maleic acid, FUMARIC ACID TECH GRADE, muconic acid.
As above containing a preparation method for unsaturated double-bond heat-resistance polyester, described ultraviolet initiator is the one in cobalt naphthenate, Cobaltous diacetate, zinc naphthenate, Zinic stearas, zinc acetate, and add-on is 0.03% ~ 0.05% of terephthalic acid weight.
Light trigger is the key ingredient of cross-linking system, and initiator molecule (250 ~ 420nm) between ultraviolet region has certain absorbing ability, and after absorbing luminous energy, initiator molecule is from ground state transition to active excited state, also can continue to transit to excited triplet state; At its excited singlet, also may be excited triplet state experience unit molecule or bimolecular chemical action after, produce can trigger monomer polymerization biologically active fragment, these biologically active fragments can be free radicals, cause crosslinking reaction.
Select metal-salt as initiator mainly because it has higher thermostability, in polymerization, spinning process, namely keep stable, cobalt salt and zinc salt react polyester and do not produce negative impact simultaneously, and cobalt salt also can be used as the toning agent of polyester.
Owing to there is unsaturated double-bond in unsaturated polyester ester molecular structure, under initiator existent condition, crosslinking reaction can be there is between the long chain molecule of unsaturated polyester and form baroque huge network molecule.Crosslinked is improve polymer performance one of most effective means, the degree of crosslinking of system can be made to raise, relative molecular mass increase, and the physical and chemical performance of polymkeric substance is significantly improved by crosslinked.
Polyester fondant degraded has two aspects to quality product impact, and namely viscosity reduces and relative molecular mass distribution broadens, and DeR is fallen PET conglutination to be affected little, but it is larger on the impact of relative molecular mass distribution, and molecular vibrational temperature is broadened.Cause the principal element of thermal destruction to be high temperature and catalyzer, high temperature is that response intensity is too high, causes degraded to be accelerated, creates end carboxyl, also make cyclic oligomer increase simultaneously; Catalyzer is then relevant to the DeR constant of catalyzer, and in polycondensation process, the effect of catalyzer is not only catalysis to generate main reaction, thus the velocity ratio and output of impact reaction, can also degrade and ehter bond generation by catalytic thermal simultaneously, increase the content of glycol ether, thus increase the content of end carboxyl.
The object of this invention is to provide a kind of polyester, adopt a relatively mild class polycondensation catalyst ethylene glycol magnesium, the less side reaction caused in reaction process is less, effectively control the less thermal destruction in the content of end carboxyl and the course of processing, decrease the generation of oligopolymer in the course of processing, also ensure that the stability of unsaturated double-bond in polyester production process simultaneously.In trevira, introduce unsaturated double-bond, and control it effectively, safely and be cross-linked, the mechanical property to trevira, resistance toheat, chemical resistance, flame retardant properties are had the raising compared with amplitude.
Beneficial effect:
● adopt ethylene glycol magnesium and antimony glycol mixture as polycondensation catalyst, ethylene glycol magnesium belongs to a comparatively gentle class, its thermal destruction coefficient is very little, the side reaction caused in reaction process is less, decrease the generation of end carboxyl and oligopolymer in the course of processing, also ensure that the stability of unsaturated double-bond in polyester production process simultaneously.
● the content of carboxyl end group of polyester slice is less than 20mol/t, and oligopolymer mass percentage content is less than 1.0%, and the mass percentage content of glycol ether is less than 1.0%, is conducive to the quality improving fiber further.Average containing 1 ~ 6 unsaturated double-bond provided by unsaturated dibasic acid molecule in described polyester macromolecular chain.
● introduce unsaturated double-bond at polyester, and after prepare by trevira, control that it is crosslinked effectively, safely, the mechanical property to trevira, resistance toheat, chemical resistance, flame retardant properties are had the raising compared with amplitude.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
One of the present invention is containing unsaturated double-bond polyester, and being terephthalic acid, unsaturated dibasic acid and ethylene glycol under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol containing unsaturated double-bond polyester, polycondensation obtains, then obtains polyester slice through pelletizing; In polyester slice, content of carboxyl end group is less than 20mol/t, and oligopolymer mass percentage content is less than 1.0%, and the mass percentage content of glycol ether is less than 1.0%; Containing average containing 1 ~ 6 unsaturated double-bond provided by unsaturated dibasic acid molecule in a macromolecular chain of unsaturated double-bond polyester; The molecular formula of ethylene glycol magnesium is Mg (OCH
2cH
2oH)
2.
Wherein, the number-average molecular weight containing unsaturated double-bond polyester is 15000 ~ 22000.
Wherein, in the mixture of ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1.
Embodiment 1
Containing a preparation method for unsaturated double-bond polyester, specifically comprise the following steps:
(1) preparation of catalyst glycol magnesium:
In single-cell, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 6V, cathode current density is 150mA, electrolysis 10 hours when 50 DEG C, and electrolysis terminates rear taking-up electrode, obtains white suspension liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation:
Esterification:
Adopt terephthalic acid, unsaturated dibasic acid maleic acid and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid is 1.2:1, unsaturated dibasic acid and terephthalic acid mol ratio are 1:100, carry out esterification, obtain esterification products after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure, and temperature is at 250 DEG C, and esterification water quantity of distillate reaches 91% of theoretical value for esterification terminal;
Polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The polycondensation rough vacuum stage, catalyzer, stablizer triphenylphosphate and ultraviolet initiator cobalt naphthenate is added in esterification products, triphenylphosphate consumption is 0.01% of terephthalic acid weight, cobalt naphthenate add-on is 0.03% of terephthalic acid weight, polycondensation is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature controls at 260 DEG C, and the reaction times is 30 minutes; Catalyzer is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 2:1; Polycondensation high vacuum stage of Fig, after the polycondensation rough vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 98Pa, and temperature of reaction controls at 275 DEG C, 50 minutes reaction times; Obtained number-average molecular weight is the polyester of 15000, obtains polyester slice through pelletizing.
Embodiment 2
Containing a preparation method for unsaturated double-bond polyester, specifically comprise the following steps:
(1) preparation of catalyst glycol magnesium:
In single-cell, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 10V, cathode current density is 200mA, electrolysis 12 hours when 60 DEG C, and electrolysis terminates rear taking-up electrode, obtains white suspension liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation:
Esterification:
Adopt terephthalic acid, unsaturated dibasic acid FUMARIC ACID TECH GRADE and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid is 2.0:1, unsaturated dibasic acid and terephthalic acid mol ratio are 5:100, carry out esterification, obtain esterification products after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.3MPa, and temperature is at 260 DEG C, and esterification water quantity of distillate reaches 95% of theoretical value for esterification terminal;
Polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The polycondensation rough vacuum stage, catalyzer, stablizer trimethyl phosphite 99 and ultraviolet initiator Cobaltous diacetate is added in esterification products, trimethyl phosphite 99 consumption is 0.05% of terephthalic acid weight, Cobaltous diacetate add-on is 0.05% of terephthalic acid weight, polycondensation is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 270 DEG C, and the reaction times is 50 minutes; Catalyzer is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 3:1; Polycondensation high vacuum stage of Fig, after the polycondensation rough vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 95Pa, and temperature of reaction controls at 280 DEG C, 90 minutes reaction times; Obtained number-average molecular weight is the polyester of 22000, obtains polyester slice through pelletizing.
Embodiment 3
Containing a preparation method for unsaturated double-bond polyester, specifically comprise the following steps:
(1) preparation of catalyst glycol magnesium:
In single-cell, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 7V, cathode current density is 160mA, electrolysis 11 hours when 55 DEG C, and electrolysis terminates rear taking-up electrode, obtains white suspension liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation:
Esterification:
Adopt terephthalic acid, unsaturated dibasic acid muconic acid and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid is 1.5:1, unsaturated dibasic acid and terephthalic acid mol ratio are 2:100, carry out esterification, obtain esterification products after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches 92% of theoretical value for esterification terminal;
Polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The polycondensation rough vacuum stage, catalyzer, stablizer trimethyl phosphite and ultraviolet initiator zinc naphthenate is added in esterification products, trimethyl phosphite consumption is 0.02% of terephthalic acid weight, zinc naphthenate add-on is 0.04% of terephthalic acid weight, polycondensation is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature controls at 265 DEG C, and the reaction times is 35 minutes; Catalyzer is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 2:1; Polycondensation high vacuum stage of Fig, after the polycondensation rough vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 96Pa, and temperature of reaction controls at 278 DEG C, 55 minutes reaction times; Obtained number-average molecular weight is the polyester of 16000, obtains polyester slice through pelletizing.
Embodiment 4
Containing a preparation method for unsaturated double-bond polyester, specifically comprise the following steps:
(1) preparation of catalyst glycol magnesium:
In single-cell, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 8V, cathode current density is 160mA, electrolysis 11 hours when 55 DEG C, and electrolysis terminates rear taking-up electrode, obtains white suspension liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation:
Esterification:
Adopt terephthalic acid, unsaturated dibasic acid maleic acid and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid is 1.5:1, unsaturated dibasic acid and terephthalic acid mol ratio are 2:100, carry out esterification, obtain esterification products after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches 95% of theoretical value for esterification terminal;
Polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The polycondensation rough vacuum stage, catalyzer, stablizer trimethyl phosphite 99 and ultraviolet initiator Zinic stearas is added in esterification products, trimethyl phosphite 99 consumption is 0.03% of terephthalic acid weight, ultraviolet initiator add-on is 0.04% of terephthalic acid weight, polycondensation is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the reaction times is 40 minutes; Catalyzer is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 3:1; Polycondensation high vacuum stage of Fig, after the polycondensation rough vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 96Pa, and temperature of reaction controls at 278 DEG C, 60 minutes reaction times; Obtained number-average molecular weight is the polyester of 18000, obtains polyester slice through pelletizing.
Embodiment 5
Containing a preparation method for unsaturated double-bond polyester, specifically comprise the following steps:
(1) preparation of catalyst glycol magnesium:
In single-cell, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 8V, cathode current density is 180mA, electrolysis 11 hours when 55 DEG C, and electrolysis terminates rear taking-up electrode, obtains white suspension liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation:
Esterification:
Adopt terephthalic acid, unsaturated dibasic acid FUMARIC ACID TECH GRADE and ethylene glycol as raw material, the mol ratio of ethylene glycol and terephthalic acid is 1.6:1, unsaturated dibasic acid and terephthalic acid mol ratio are 4:100, carry out esterification, obtain esterification products after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.1MPa, and temperature is at 255 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The polycondensation rough vacuum stage, catalyzer, stablizer trimethyl phosphite 99 and ultraviolet initiator zinc acetate is added in esterification products, trimethyl phosphite 99 consumption is 0.03% of terephthalic acid weight, zinc acetate add-on is 0.03% of terephthalic acid weight, polycondensation is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure 492Pa by normal pressure, and temperature controls at 264 DEG C, and the reaction times is 40 minutes; Catalyzer is the mixture of ethylene glycol magnesium and antimony glycol, and ethylene glycol magnesium and antimony glycol mass ratio are 3:1; Polycondensation high vacuum stage of Fig, after the polycondensation rough vacuum stage, continues to vacuumize, makes reaction pressure be down to absolute pressure 96Pa, and temperature of reaction controls at 276 DEG C, 70 minutes reaction times; Obtained number-average molecular weight is the polyester of 21000, obtains polyester slice through pelletizing.
Claims (10)
1. one kind contains unsaturated double-bond polyester, it is characterized in that: be describedly terephthalic acid, unsaturated dibasic acid and ethylene glycol under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol containing unsaturated double-bond polyester polycondensation obtains, then obtain polyester slice through pelletizing;
In described polyester slice, content of carboxyl end group is less than 20mol/t, and oligopolymer mass percentage content is less than 1.0%, and the mass percentage content of glycol ether is less than 1.0%; Described containing average containing 1 ~ 6 unsaturated double-bond provided by unsaturated dibasic acid molecule in a macromolecular chain of unsaturated double-bond polyester;
The molecular formula of described ethylene glycol magnesium is Mg (OCH
2cH
2oH)
2.
2. one according to claim 1 is containing unsaturated double-bond polyester, it is characterized in that, the described number-average molecular weight containing unsaturated double-bond polyester is 15000 ~ 22000.
3. one according to claim 1 is containing unsaturated double-bond polyester, and it is characterized in that, in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1.
4. a kind of preparation method containing unsaturated double-bond polyester according to any one of claims 1 to 3, it is characterized in that: the polycondensation under esterification and the mixture through catalytic effect at ethylene glycol magnesium and antimony glycol of terephthalic acid, unsaturated dibasic acid and ethylene glycol obtains polyester, then obtains polyester slice through pelletizing.
5. a kind of preparation method containing unsaturated double-bond polyester according to claim 4, is characterized in that specifically comprising the following steps:
(1) preparation of catalyst glycol magnesium:
In single-cell, add ethylene glycol, supporting electrolyte is magnesium chloride, and metal MAG block is anode, and negative electrode is graphite; Logical direct current, starting voltage 6 ~ 10V, cathode current density is 150 ~ 200mA, electrolysis 10 ~ 12 hours when 50 ~ 60 DEG C, and electrolysis terminates rear taking-up electrode, obtains white suspension liquid; Filtration under diminished pressure, white solid absolute ethanol washing, obtains ethylene glycol magnesium after drying;
(2) preparation of polyester, comprises esterification and polycondensation:
Described esterification:
Adopt terephthalic acid, unsaturated dibasic acid and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure ~ 0.3MPa, and temperature is at 250 ~ 260 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, catalyzer, stablizer and ultraviolet initiator is added in esterification products, polycondensation is started under the condition of negative pressure, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature controls at 260 ~ 270 DEG C, and the reaction times is 30 ~ 50 minutes; Described catalyzer is the mixture of ethylene glycol magnesium and antimony glycol;
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and temperature of reaction controls at 275 ~ 280 DEG C, 50 ~ 90 minutes reaction times;
Obtained polyester, obtains polyester slice through pelletizing.
6. a kind of preparation method containing unsaturated double-bond polyester according to claim 4 or 5, it is characterized in that, the mol ratio of described ethylene glycol and described terephthalic acid is 1.2 ~ 2.0:1.
7. a kind of preparation method containing unsaturated double-bond polyester according to claim 5, it is characterized in that, in the mixture of described ethylene glycol magnesium and antimony glycol, ethylene glycol magnesium and antimony glycol mass ratio are 2 ~ 3:1; Described catalyst levels is 0.01% ~ 0.05% of described terephthalic acid quality.
8. a kind of preparation method containing unsaturated double-bond polyester according to claim 5, it is characterized in that, described stablizer is selected from the one in triphenylphosphate, trimethyl phosphite 99 and trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.05% of terephthalic acid weight.
9. a kind of preparation method containing unsaturated double-bond polyester according to claim 5, it is characterized in that, described unsaturated dibasic acid and terephthalic acid mol ratio are 1 ~ 5:100; Described unsaturated dibasic acid is the one in maleic acid, FUMARIC ACID TECH GRADE, muconic acid.
10. a kind of preparation method containing unsaturated double-bond polyester according to claim 5, it is characterized in that, described ultraviolet initiator is the one in cobalt naphthenate, Cobaltous diacetate, zinc naphthenate, Zinic stearas, zinc acetate, and add-on is 0.03% ~ 0.05% of terephthalic acid weight.
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| US11174346B2 (en) * | 2015-12-29 | 2021-11-16 | Jiangsu Hengli Chemical Fibre Co., Ltd. | Flame-retardant polyester fiber and its preparation method |
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| CN115107341A (en) * | 2022-08-08 | 2022-09-27 | 江苏裕兴薄膜科技股份有限公司 | High-transmittance low-fog optical base film and preparation method thereof |
| CN115107341B (en) * | 2022-08-08 | 2024-05-31 | 江苏裕兴薄膜科技股份有限公司 | High-transmittance low-fog optical base film and preparation method thereof |
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