CN109456467A - Improve the preparation method of flexible polycyclohexylene's diformazan alcohol ester resin - Google Patents
Improve the preparation method of flexible polycyclohexylene's diformazan alcohol ester resin Download PDFInfo
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- CN109456467A CN109456467A CN201811030182.1A CN201811030182A CN109456467A CN 109456467 A CN109456467 A CN 109456467A CN 201811030182 A CN201811030182 A CN 201811030182A CN 109456467 A CN109456467 A CN 109456467A
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- 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
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- 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
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- 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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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- 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
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- 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
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C08K5/00—Use of organic ingredients
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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Abstract
The present invention relates to the preparation methods for improving flexible polycyclohexylene's diformazan alcohol ester system resin, resin combination puts into following structural element, by dimethyl terephthalate (DMT) in the structural element, the molar ratio of compounds and the glycol such as the dicarboxylic acids of or mixtures thereof phthalic acid composition and three alcoholic compounds is 1:1.05 up to 1:2.5 or less, on the basis of the molar ratio of above-mentioned dicarboxylic acid mixture, add neopentyl glycol 1% to 10%, thus can get not only makes the property of resin become flexible, and polycyclohexylene's diformazan alcohol ester resin that durability is strengthened.
Description
Technical field
The present invention is related to improving flexible polycyclohexylene's diformazan alcohol ester (hereinafter, ' PCT') resin
Flexibility is more compared with previous PCT resin while the invention of preparation method, the more specifically high-fire resistance of maintenance PCT resin
Add raising, thus there is as easy exploitation purposes and be applicable to the characteristic of a variety of industrialized copolymers (copolymer)
PCT resin preparation method invention.
Background technique
PCT resin is usually that polyakylene terephthalate (Polyalkylene terephthalat e) is resin
One kind, above-mentioned polyakylene terephthalate system resin are censured under the presence of regulation catalyst, as Polyester to benzene two
Formic acid (Terephthalic acid, TPA) or dimethyl terephthalate (DMT) (Dimethyl terephthalate, DMT) and alcohol
Ingredient alkylen glycol compound carries out esterification and polymerization and the high-molecular compound that generates.
Heat resistance when this polyakylene terephthalate system resin has macromolecule resin compared with PP, PE etc, thoroughly
The outstanding feature of the various physical property such as bright property, intensity, processability.
This polyakylene terephthalate system resin can divide into poly- terephthaldehyde according to the type of alcohol component (glycol)
Sour glycol ester (Polyethylene terephthalate, " PET ") resin, polypropylene terephthalate
(Polytrimethylene terephthalate, " PTT ") resin, polybutylene terephthalate (PBT) (Polybutylene
Terephthalate, " PBT ") resin, polycyclohexylene's diformazan alcohol ester (Polycyclohexylenedimethyl
Ene terephthalate, " PCT ") resin etc..
PET resin uses ethylene glycol (Ethyleneglycol) as alcohol component (glycol), and PTT resin uses 1,3- the third two
Alcohol (1,3-Propanediol) be used as alcohol component (glycol), PBT resin use 1,4-butanediol (Isosorbide-5-Nitrae-Butanediol) as
Alcohol component (glycol), and PCT resin uses 1,4-CHDM (1.4-Cyclohexane dimethanol, CHDM)
As alcohol component.
Polyakylene terephthalate system resin usually has the homopolymer (Homopolymer) being made of single alcohol component
Form, but according to alcohol component, have any different in the various physical property such as fusing point, crystallinity, heat resistance, intensity of macromolecule resin,
It, can also be using glycol of more than two kinds as the copolyesters (Copolyester) or of more than two kinds of raw polyol according to required physical property
Homopolymer is produced in the form of being mutually mixed.
Although PET has outstanding physical property, fusing point is low, is limited, and also fusing point is too low by PBT, is not suitable for being suitable for precision
Chemistry or functional high-polymer engineering plastics, so the technology that mixes of the resin high with fusing point is flourishing, this with high-fire resistance
Thermal decomposition can occur when mixing for resin and color continues the problem of declining.
As described above, polyakylene terephthalate system resin usually has the shape for the homopolymer being made of single alcohol component
State, the selected alcohol for being suitable for the form, synthetic copolymer need to maintain high-fire resistance and improve flexible technology.
PCT regardless of having been developed that long, but in use on much limited.In particular, not yet finding the suitable use of PCT
On the way, it in the field for needing the functional engineering plastics of the resin of high-fire resistance recently, is gradually increased using degree.For example, exploitation
LED TV, electric vehicle etc., high-fire resistance resin need to increase therewith (for example, being used as light reflecting board in LED TV, electronic
It is used as connector in vehicle), actually its needs is also continuing growing.
The characteristic for further watching other above-mentioned resins, using the homopolymer of single component system (single glycol) as base
Standard is watched, and (256 DEG C) of fusing point of PET resin are high, and the physical property such as the transparency, intensity are outstanding, are utilized as including that plastic containers exist extensively
Interior general-purpose plastics, but since crystallization rate is relatively low, the engineering plastics purposes of the crystallinity high as needs is limited.
For PBT resin compared with PET resin, crystallization rate is fast, and physical property is also outstanding, is suitable as engineering plastics purposes, but
It is fusing point is 225 DEG C, it is relatively lower than PET resin (256 DEG C), as needing the plastic applications of heat resistance limited.
In contrast, the fusing point of PCT resin is 290 DEG C or more, compared with PBT resin (225 DEG C) or PET resin (256 DEG C),
Heat resistance is very outstanding, and crystallization rate is also fast, and dimensional stability (dimensional stability) is also outstanding, is classified as surpassing
Grade engineering plastics (super eng ineering plastic).
Moreover, the producing cost of PCT resin also relative moderate, for example, compared with competing plastic product, production prices
PCT resin is utilized as being used in electricity/electronics special connector, rel ay (relay), surface installation socket, have in vapour
The harness socket and engine hatch cover in car engine cabin, LED TV backlight reflection plate material.
PCT resin, can be to the phthalic acid (TPA) or right as sour component under the presence of titanium system or tin series catalysts
Rutgers (DMT) and as alcohol component 1,4 cyclohexane dimethanol (CHDM) carry out esterification or transesterification it is anti-
It should and carry out condensation polymerization and obtain.As reference, PCT resin originally develops production in U.S. Yi Shiman (EASTMAN) company,
It in 2000 by Du Pont (DUPONT) corporate buyout, is sold currently as trade (brand) name trie smooth (TRITANTM), the country is in SKization
Company production.
PCT resin not only includes the PCT resin prepared by 1,4-CHDM single component as sour component, but also
Xenogenesis alcohol comprising the 1,4 cyclohexane dimethanol as principal component in sour component and the ethylene glycol as accessory ingredient etc at
The polyester copolymer divided.
PCT resin, especially homopolymer PCT resin are the high-fire resistance resins that fusing point is 290 DEG C or more.PCT resin ratio
PET, PBT etc. are played, crystallinity is high, and is high-fire resistance, but in the characteristic of resin, reduction of pliability, in purposes exploitation
It is much limited, the flexible demand for thus improving PCT resin gradually increases in the art.
Summary of the invention
The present invention is as above for solving the problems, such as, the object of the present invention is to provide the flexibility in order to improve PCT resin,
Using polyalcohol, in order to prevent therewith bring reactivity reduce and color change, using catalyst and compound stabilizer, thus
The preparation method of flexibility and the outstanding polycyclohexylene's diformazan alcohol ester system resin of color.
The present invention is put into 1:1.1~1:2.0 molar ratio by dimethyl terephthalate (DMT), benzene diformazan in SUS reactor
The dicarboxylic acid derivatives compound and 1,4- hexamethylene two when using diol compound molal quantity as benchmark of or mixtures thereof acid composition
Methanol content is the diol compound of 90mol% or more, on the basis of above-mentioned dicarboxylic acid derivatives compound molal quantity, addition 2
To the alcohol of the ethylene glycol of 10 moles of %, diethylene glycol, 1,4- butanediol, 1,3- propylene glycol, neopentyl glycol, 1,6-HD etc..
As above-mentioned dimethyl terephthalate (DMT) and above-mentioned phthalic acid, exquisiteness terephthalic acid (TPA) (PTA, Purified can be used
Terephthalic Acid).Wherein, carboxylic acid previous phthalic acid include 1 or more isophathalic acid, 2,6 dicarboxylic acids of naphthalene,
It polymerize within 2~10 moles of % of the acid type such as dimethyl isophathalic acid.So after investment raw material, oxidation stabilizers and heat are put into
Stabilizer blocks air to enter in the reactor for putting into catalyst again in the case where nitrogen cleans (Purge).
At this point, applying 2kg/cm to completely remove the oxygen in reactor2Nitrogen pressure, be vented (vent), apply again
Nitrogen pressure, once exhaust, the oxygen being completely removed in reactor.Very due to ester exchange reaction and esterification or polymerization temperature
Height, therefore can be aoxidized having a small amount of oxygen, color is degenerated or is thermally decomposed, but as described above, completely removes reactor
Thus interior oxygen can prevent color from declining and thermally decomposing as far as possible.
In the state of so barrier oxygen, the heating for ester exchange reaction and esterification is executed, wherein if heated
Fastly, then there is the danger of the worry and color change dispersed, on the contrary, reaction speed is slack-off if heated slow, not only reduce life
Efficiency is produced, and it is high to form high molecular probability in the polymerization.So in starting step, heating 7 per minute~
It is effective at 10 DEG C, after 20 minutes, heat up per minute 3~5 DEG C or so when it is ideal.
At 270 DEG C~300 DEG C, esterification or ester exchange reaction are carried out, after generating oligomer, monomer is transferred to
Polymer reactor, this is must to be pressurizeed and be transferred with nitrogen, wherein if applying excessively high pressure, burn danger occurs or splashes
On wall, therefore 0.5kg/cm2When it is appropriate.Polycyclohexylene's diformazan alcohol ester is provided in this specification below
It is the preparation method of resin, which is characterized in that under 285 DEG C~320 DEG C vacuum reactions, polycondensation is carried out to the monomer so transferred
Close reaction.
In above-mentioned diol compound, the remaining diol compound other than 1,4-CHDM, which can be, to be selected from
One or more of ethylene glycol, 1,3-PD, 1,4-butanediol, neopentyl glycol, 1,6- hexylene glycol, the content is with whole glycol
It may include for 2~10mol% or less on the basis of compound molal quantity.
It also may include a small amount of different phthalein as isomers as dicarboxylic acid component to improve PCT system resin of the invention
Sour (Isophthalic acid) and polymerize.Wherein, the content of isophathalic acid is with above-mentioned dicarboxylic acid derivatives compound molal quantity
Benchmark preferably includes 0.1~10mol%.
Preferably, in whole input amount, above-mentioned catalyst 10ppm~100ppm is put into, above-mentioned catalyst is selected from by oxygen
Change titanium, tetraethyl titanate, four n-propyl of metatitanic acid, tetraisopropyl titanate, tetra-n-butyl titanate, tetrabutyl titanate, metatitanic acid butyl
The titanium system of isopropyl ester, the tin system of Dibutyltin oxide (Dibutyltineoxide), manganese acetate, cobalt acetate, calcium acetate, zinc acetate
One or more of group of composition.
Preferably, above-mentioned oxidation stabilizers filter out selected from by trimethyl phosphate (Tri-meth ylphosphate),
Triethyl phosphate (Tri-ethylphosphate), two aryloxy group triguaiacyl phosphate (neopentyl of neopentyl
Diaryloxytriphosphate), triphenyl (Tri-phenylphosphate), phosphonoacetate
(Tri-ethylphosphonoacetate), phosphoric acid (Phosphoric acid) or phosphorous acid (Phosphorous acid) group
At one or more of group type, put into 20ppm~120ppm of PCT entirety input amount.
In the present invention, the dominant alternative solved the problems, such as, which is characterized in that use polyalcohol, form copolymer, improve soft
Toughness is especially quantized in a manner of flexible in the property for measuring resin using UTM.Need intrinsic viscosity 0.5~
The value (numerical value is higher, outstanding) of 80 or more 1.2dl/g, col-L, 6 the following value of col-b (numerical value is lower, outstanding) preferably,
UTM value is intensity: 38~40.2mps, elongation percentage: 200~220%, spring rate: when numerical value in 247~252mps, spring rate
It is outstanding.
The present invention is in general polycyclohexylene's diformazan alcohol ester process for preparing resins, using the alcohol kind of multiplicity
Class improves flexibility, and PCT resin prepared in accordance with the present invention is improved compared with previous PCT resin, flexibility, poly- to benzene
In dioctyl phthalate cyclohexanedimethanoester ester preparation process use composite catalyst and compound stabilizer, thus prevent reactivity reduce with
Color is bad.
Be also easy to be suitable for because above-mentioned reason is difficult to develop electric power connector, socket, SMT of purposes etc., also can be used in
Heat sink, automobile motor lid, thermoregulator etc., it is therefore contemplated that it is applied.
Detailed description of the invention
Fig. 1 shows the schematic diagrames of omnipotent physical property test machine (UTM).
Specific embodiment
In the present invention, term " polycyclohexylene's diformazan alcohol ester system resin (PCT system resin) " not only includes
It as the PCT resin of homopolymer, and again include PCT polyester copolymer (Copolyester).PCT resin is intended as two
Alcohol component, is polymerized alone resin obtained by 1,4-CHDM, and PCT polyester copolymer means in addition to Isosorbide-5-Nitrae-hexamethylene two
Other than methanol, it is polymerized together by ethylene glycol, 1,3-PD, 1,4-butanediol, neopentyl glycol, 1,6- hexylene glycol etc. more
Ingredient system PCT resin.In the present invention, above-mentioned ethylene glycol, 1,3-PD, 1,4-butanediol, neopentyl glycol, 1,6- oneself two
Alcohol has 10mol% or less on the basis of whole glycol molal quantity.In the present invention, PCT system resin is in diol component, and 1,
4- cyclohexanedimethanol content is 90mol% or more, and neopentyl glycol content within 10 moles of % to prepare.
The present inventor also improves durability by the flexibility of raising PCT resin, in order to which also application is electric electronics, electricity
The metal replacements such as motor-car are used, and research PCT is resin modified as a result, especially focusing on, compared with previous PCT monomer component, no
It is only used in combination alcohol component, and the polyalcohol influenced, composite catalyst and compound can be brought on reactivity or color change
Stabilizer is selected.
The present invention propose polycyclohexylene's diformazan alcohol ester resin preparation method, in reactor, comprising
The diol compound of 1,4-CHDM, the acid comprising phthalic acid or dimethyl benzene dioctyl phthalate, the dicarboxylic acids of isophathalic acid
In the value that class/glycol (glycol) class is polymerize on the basis of below mole of % of 1:1.1 to 1:3, intrinsic viscosity (Intrinsic
Viscosity) value is 0.4~1.2dl/g, and UTM value is intensity: 38~40.2mps, elongation percentage: 200~220%, spring rate:
247~252mps value is 80 or more col-L, col-b 5 hereinafter, outstanding and spring rate is improved.
In order to obtain above-mentioned high-molecular compound, selected catalyst is particularly important, the catalysis of the following type in catalyst
Agent helps to react.Preferably, selected from by titanium oxide, butyl titanate, four n-propyl of metatitanic acid, tetraisopropyl titanate, metatitanic acid four
N-butyl, tetrabutyl titanate, the titanium system of metatitanic acid butyl isopropyl ester, Dibutyltin oxide (Dibutyltineoxide) tin
In the group that system, manganese acetate, zirconium acetate, calcium acetate, zinc acetate form, other than titanium oxide, it is at least used in mixed way a kind or more
It is effective when about 10%~30%, it is preferable that merge two types, in former auxiliary material input amount, account between 50ppm~400ppm.
If catalyst input amount be 50ppm hereinafter, if the reaction time it is elongated, not only become productivity problem, if but also when
Between it is too long, can also become color change and producing high-molecular problem, if catalyst input amount be 400ppm or more, the reaction time contracting
It is short, it is difficult to adjust color instead, there are rotten worries when placing under long-time room temperature after commercialization, urge so which kind of is selected
Agent becomes major issue.
As reference, if using catalyst stabilizer must be used, also in order to prevent from reacting by using polyalcohol
Property reduce, it is particularly important using compound stabilizer as using composite catalyst.As the type of stabilizer, there is front three
Base phosphate (Tri-methylphosphate), triethyl phosphate (Tri-ethylphosphate), two aryloxy group three of neopentyl
Phosphate (neopentyl diaryloxytriphosphate), triphenyl (Tri-phenylphosphate), phosphorus
Acyl acetic acid triethyl (Tri-ethylphosphonoacetate), phosphoric acid (Phosphoric acid), phosphorous acid
(Phosphorous acid) etc. is preferably used in mixed way trimethyl phosphate (Tri-methylphosphate), phosphoric acid
(Phosphoric acid), phosphoric acid (Phosphoric acid) suitably account for trimethyl phosphate (Tri-
Methylphosphate) 10~30%.
In this way, the sum of two types are preferably 70ppm~500ppm in whole input amount, if investment 70ppm hereinafter, if
Reaction time shortens, and is difficult to adjust color, if investment 500ppm or more, though adjustable color, the reaction time is slack-off,
Productivity reduces, therefore selected stabilizer, suitably puts into trimethyl phosphate (Tri-methylphosphate) and phosphoric acid together
(Phosphoric acid) is particularly important.
It will be carried out 2~3 minutes or so in above-mentioned acids and glycols, before starting reaction in reactor
Nitrogen cleans (Purge), this helps to optimize color.
Secondly, improving temperature, if excessively steeply rising temperature, color can disperse before occurring or reacting.Therefore, excellent
Selection of land gradually increases temperature as far as possible, if being only excessively slowly increased temperature, can cause productive decline.Preferably, it reacts
After beginning, 30~50/, it is adjusted to reach initial point (time point for occurring by-product for the first time), the reaction time is from the beginning of
To time point is terminated, preferably 120 points to 240/, reaction temperature is preferably adjusted between 270 DEG C~300 DEG C.If initial
Point is excessively to steeply rise temperature within 30 minutes, can disperse, and by 50 timesharing, reaction extends, and monomer reaction excessively extends, and is tied
Fruit can reduce productivity.
If total reaction time is within 120 points, the reaction time shortens, and acid value (COOH value) is high, in the polymerization, has
Macromolecule may not be formed, if total reaction time is 240 points or more, there is a possibility that color can become, productivity reduces, can be right
Expense is brought a negative impact.For reaction pressure, even if even dimethyl terephthalate (DMT) reacts at normal temperature, but benzene
(the 1kg/cm even if dioctyl phthalate is pressurizeed2) reaction can also obtain result.The monomer that such polymerize is obtained is transferred to poly-
When closing reactor, it is necessary to be transferred with nitrogen, could there is no color change, and also contribute to fire prevention.In order to will so move
The monomer reaction stipulated time sent, it is polymerize in a short time, needs to carry out vacuum reaction, but since initial stage molecular weight is low,
Therefore it is critically important slowly to carry out low vacuum reaction.
In the past, manual fine-tuning triple valve, but the solenoid valve based on computer program is used recently, it can reach in 30 minutes
760mmHg~20mmHg is divided into about 10 points, 20mmHg~vacuum later, and when polymerization can become ideal reaction.Wherein, very
Reciprocal of duty cycle prepares polycyclohexylene's diformazan alcohol ester resin between 0.01 support (torr)~1 support (torr), this is to high score
Son is good, when polymerization reaction, the reaction time can according to the type of resin, catalyst, stabilizer and differ widely, but polymerize anti-
It answers, is suitably 100 points~300 points in the total polymerization reaction time.
Most preferably, when preparing polymer, it polymerize under the reaction temperature between 290 DEG C~320 DEG C, if 290 DEG C
Hereinafter, being then difficult to polymerize, fusing point is high, there is cured worry, if 320 DEG C or more, is then easy thermal decomposition.Therefore, if reaching institute
Need degree, then carry out high temperature polymerization, if therefore terminate polymerization, got outside reactor within the faster time, such ability
It prevents from thermally decomposing as far as possible.At least the reaction time terminates, and within 30 points, if do not taken out out of reactor, because of thermal decomposition, divides
Son amount also reduces, and color also becomes, it is difficult to and using is product, so must be discharged in a short time critically important.
Batchwise polymerization method (Batch polymerization) is implemented in experiment in the present invention, into extensive capital equipment
When can be implemented continuous polymerization (Continuous polymerization) and batchwise polymerization method (Batch
Polymerization, hereinafter referred to as Bx), as a reference, preferably, batchwise polymerization method is carried out until 2000 tons, if
2000 tons or more, then preferably continuous polymerization (Continuous polymerization, hereinafter referred to as C.P) mode.C.P work
Skill initial stage is difficult to impose a condition, but once imposes a condition, and can not only save labour cost, but also more easily quality management, than
Bx formula is played, the color of C.P technique is welcome.
(chemical structural formula)
Embodiment 1.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 595g (4.132g mol), neopentyl glycol 8.784 (0.08g mol), titanium oxide 0.397g, butyl titanate
After 0.04g, trimethyl phosphate 0.49g, phosphorous acid 0.05g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure,
It is repeated 3 times exhaust (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached about 160
DEG C between 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reaction
Device is polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points or so
Vacuum reaction, discharge.
Embodiment 2.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 582.93g (4.05g mol), neopentyl glycol 17.54g (0.168g mol), titanium oxide 0.353g, butyl titanate
After 0.08g, trimethyl phosphate 0.44g, phosphorous acid 0.11g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure,
It is vented (Vent), applies nitrogen pressure again, be repeated 3 times exhaust (Vent), cover heating after reactor cap.It is separated about 30~40
Carry out by-product, temperature is reached between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product
All outflows, then be transferred to PA reactor, polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is
300 DEG C, about 100 points or so of vacuum reaction is carried out, is discharged.
Embodiment 3.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 570.78g (3.96g mol), neopentyl glycol 26.31g (0.25g mol), titanium oxide 0.308g, butyl titanate
After 0.132g, trimethyl phosphate 0.38g, phosphorous acid 0.16g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure,
It is vented (Vent), applies nitrogen pressure again, be repeated 3 times exhaust (Vent), cover heating after reactor cap.It is separated about 30~40
Carry out by-product, temperature is reached between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product
All outflows, then be transferred to PA reactor, polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is
300 DEG C, about 100 points or so of vacuum reaction is carried out, is discharged.
Embodiment 4.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 558.64g (3.87g mol), neopentyl glycol 35.08g (0.34g mol), titanium oxide 0.308g, butyl titanate
After 0.132g, trimethyl phosphate 0.38g, phosphorous acid 0.16g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure,
It is vented (Vent), applies nitrogen pressure again, be repeated 3 times exhaust (Vent), cover heating after reactor cap.It is separated about 30~40
Carry out by-product, temperature is reached between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product
All outflows, then be transferred to PA reactor, polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is
300 DEG C, about 100 points or so of vacuum reaction is carried out, is discharged.
Embodiment 5.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), titanium oxide 0.308g, butyl titanate
After 0.132g, trimethyl phosphate 0.38g, phosphorous acid 0.16g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure,
It is vented (Vent), applies nitrogen pressure again, be repeated 3 times exhaust (Vent), cover heating after reactor cap.It is separated about 30~40
Carry out by-product, temperature is reached between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product
All outflows, then be transferred to PA reactor, polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is
300 DEG C, about 100 points or so of vacuum reaction is carried out, is discharged.
Comparative example 1.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
After alkane dimethanol 607.2g (4.217g mol), titanium oxide 0.442g, trimethyl phosphate 0.55g etc., in order to go deoxygenation, benefit
With nitrogen, apply 1kg/cm2Pressure, be vented (Vent), again apply nitrogen pressure, be repeated 3 times exhaust (Vent), covering reactor cap it
After heat up.By-product is branched away about 30~40, temperature is reached between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points
Left and right reacted, if by-product all flow out, be transferred to PA reactor, polymerize, at this point, vacuum degree be 0.001 to
Between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points or so of vacuum reaction, is discharged.
Comparative example 2.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 595g (4.132g mol), neopentyl glycol 8.784g (0.08g mol), titanium oxide 0.442g, phosphorous acid 0.55g etc.
Later, in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times exhaust
(Vent), reactor cap is covered to heat up later.Branch away by-product about 30~40, by temperature reach about 160 DEG C to 180 DEG C it
Between, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are polymerize,
At this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points or so of vacuum reaction, is arranged
Out.
Comparative example 3.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 595g (4.132g mol), neopentyl glycol 8.784g (0.08g mol), titanium oxide 0.397g, butyl titanate
After 0.04g, trimethyl phosphate 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), then
Secondary application nitrogen pressure, is repeated 3 times exhaust (Vent), covers heating after reactor cap.By-product is branched away about 30~40, it will be warm
Degree reaches between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are moved
It send to PA reactor, is polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, is carried out about
100 points or so of vacuum reaction, discharge.
Comparative example 4.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 595g (4.132g mol), neopentyl glycol 8.784g (0.08g mol), titanium oxide 0.442g, trimethyl phosphate
After 0.49g, phosphorous acid 0.05g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), applies again
Nitrogen pressure is repeated 3 times exhaust (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached
Between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA
Reactor is polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points of left sides
Right vacuum reaction, discharge.
Comparative example 5.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 595g (4.132g mol), neopentyl glycol 8.784g (0.08g mol), titanium oxide 0.397g, butyl titanate
After 0.04g, phosphorous acid 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), applies again
Nitrogen pressure is repeated 3 times exhaust (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached
Between about 160 DEG C to 180 DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA
Reactor is polymerize, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points of left sides
Right vacuum reaction, discharge.
Embodiment 1. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), tetraethyl titanate 0.442g, TMP
After 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times
It is vented (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached about 160 DEG C to 180
Between DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are carried out
Polymerization, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, and it is anti-to carry out about 100 points or so of vacuum
It answers, is discharged.
Embodiment 2. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), tetraethyl titanate 0.442g, PA
After 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times
It is vented (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached about 160 DEG C to 180
Between DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are carried out
Polymerization, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, and it is anti-to carry out about 100 points or so of vacuum
It answers, is discharged.
Embodiment 3.
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), tetra-n-butyl titanate 0.442g, TMP
After 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times
It is vented (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached about 160 DEG C to 180
Between DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are carried out
Polymerization, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, and it is anti-to carry out about 100 points or so of vacuum
It answers, is discharged.
Embodiment 4. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), tetra-n-butyl titanate 0.442g, PA
After 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times
It is vented (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached about 160 DEG C to 180
Between DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are carried out
Polymerization, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, and it is anti-to carry out about 100 points or so of vacuum
It answers, is discharged.
Embodiment 5. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), tetrabutyl titanate 0.442g, TMP
After 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times
It is vented (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached about 160 DEG C to 180
Between DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are carried out
Polymerization, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, and it is anti-to carry out about 100 points or so of vacuum
It answers, is discharged.
Embodiment 6. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), tetrabutyl titanate 0.442g, PA
After 0.55g etc., in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times
It is vented (Vent), covers heating after reactor cap.By-product is branched away about 30~40, temperature is reached about 160 DEG C to 180
Between DEG C, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are carried out
Polymerization, at this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, and it is anti-to carry out about 100 points or so of vacuum
It answers, is discharged.
Embodiment 7. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), Tio2 0.442g, TMP 0.55g etc.
Later, in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times exhaust
(Vent), reactor cap is covered to heat up later.Branch away by-product about 30~40, by temperature reach about 160 DEG C to 180 DEG C it
Between, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are polymerize,
At this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points or so of vacuum reaction, is arranged
Out.
Embodiment 8. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), Tio2 0.442g, PA 0.55g etc. it
Afterwards, in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times exhaust
(Vent), reactor cap is covered to heat up later.Branch away by-product about 30~40, by temperature reach about 160 DEG C to 180 DEG C it
Between, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are polymerize,
At this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points or so of vacuum reaction, is arranged
Out.
Embodiment 9. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), TBT 0.442g, TMP 0.55g etc. it
Afterwards, in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times exhaust
(Vent), reactor cap is covered to heat up later.Branch away by-product about 30~40, by temperature reach about 160 DEG C to 180 DEG C it
Between, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are polymerize,
At this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points or so of vacuum reaction, is arranged
Out.
Embodiment 10. (table 2)
In the case where nitrogen cleans (Purge), phthalic acid 500g (3.012g mol), Isosorbide-5-Nitrae-hexamethylene are put into esterifier
Alkane dimethanol 546.50g (3.79g mol), neopentyl glycol 43.85g (0.42g mol), TBT 0.442g, PA 0.55g etc. it
Afterwards, in order to go deoxygenation, using nitrogen, apply 1kg/cm2Pressure is vented (Vent), is applied nitrogen pressure again, is repeated 3 times exhaust
(Vent), reactor cap is covered to heat up later.Branch away by-product about 30~40, by temperature reach about 160 DEG C to 180 DEG C it
Between, by-product outflow.About 180 points or so are reacted, if by-product all flows out, are transferred to PA reactor, are polymerize,
At this point, vacuum degree is 0.001 between 1.0torr, reaction temperature is 300 DEG C, carries out about 100 points or so of vacuum reaction, is arranged
Out.
Intrinsic viscosity evaluation
Embodiment 1 to 5 and comparative example 1 to 5 measure intrinsic viscosity (IV).
As measuring method, the PCT resin of the concentration of 1.2dl/g is put into o- chlorophenol (chlorophenol),
At 70~80 DEG C, after 60 points~90 points or so carry out weight soup heating, it is completely dissolved, lets cool to room temperature, be put into 30 DEG C
Viscocity tube is surveyed to measure using Ubbelohde (Ubbelohde) capillary viscometer (Capillary Viscometer)
It is fixed, it by such as following formula, measures specific viscosity (Specific Viscosity), measures intrinsic viscosity.
* specific viscosity (η sp)=(t-t0)/t0
(wherein, t is that solvent passes through the time required when viscosmeter internal rules section；T0 measures solution by same zone
Between time)
* intrinsic viscosity [η]={ (1+4A η sp)1/2-1}/2AC
(wherein, A is 0.247, c as concentration value, is 1.2dl/g as Huggins (Huggins) constant)
Test example 2
Tensile strength/elongation percentage evaluation
In the present embodiment, in order to evaluate the tensile strength and elongation percentage of PCT resin, UTM (omnipotent physical property test is used
Machine).The size of sample is prepared as shown in the figure according to D630-4.Test speed is measured with the speed of 1mm/min, is being measured
In the process, the part Fmax with peak is set to " tensile strength ", by the slope of the chart during initial stage Flexible change
It is set to " spring rate ", in the time point that sample finally destroys, Emax is defined as " elongation percentage "." tensile strength: F ", " spring rate:
MOE " and the following mathematical expression of " elongation percentage: E " amine calculate.
* tensile strength W/Ao (W=intensity, Ao=initial stage sectional area)
* spring rate MOE=Δ W/ Δ E
* (variable quantity of Δ L=length, L=measure the length of time point, Lo=initial stage to elongation percentage Δ L/Lo=(L Lo)/Lo
Length)
(referring to following table 1)
For the research purpose of experiment, with same power value, reaction was completed, as far as possible identical intrinsic viscosity (IV,
Intrinsic Viscosity) under, find out the variation of elastic force.
Even identical power value, small difference can be also presented in IV value, and the small difference of above-mentioned degree is considered as phase
Even with commodity, digitization is carried out to it.
The data as shown in following table 1 it is found that glycol (Glycol) and CHDM is used alone with it, not as good as using two kinds with
On, it thus can confirm that spring rate increases, in the case where two or more, elongation percentage also more increases, so be easier to prepare
High-fire resistance fiber can contribute to the diversification of purposes significantly.
(referring to following table 2)
The difference of Tables 1 and 2 is that table 1 is physical property variation and quality versus based on CHDM and NPG content, with this phase
Instead, the regulation of table 2 ground maintains CHDM and NPG content, for the number based on the physical property of catalyst and stabilizer comparison and quality versus
According to.
Table 1
Above-mentioned table abbreviation: 1,4-CHDM (CHDM, Isosorbide-5-Nitrae-Cyclohexane dime thanol), new penta 2
Alcohol (NPG, Neopentylglycol), trimethyl phosphate (TMP, Trimethylphosphoricacid), butyl titanate
(TBT, Tetrabutyltitanate), phosphorous acid (PA, Phosphorous Acid), COL L (white, White), b (micro- Huang
Color, Yellowish)
Table 2
Above-mentioned table abbreviation: 1,4-CHDM (CHDM, Isosorbide-5-Nitrae-Cyclohexane dime thanol), new penta 2
Alcohol (NPG, Neopentylglycol), trimethyl phosphate (TMP, Trimethylphosphoricacid), butyl titanate
(TBT, Tetrabutyltitanate), phosphorous acid (PA, Phosphorous Acid), COL L (white, White), b (micro- Huang
Color, Yellowish)
Claims (11)
1. a kind of preparation method of polycyclohexylene's diformazan alcohol ester resin, which is characterized in that
Include:
It in the reactor, include 1,4-CHDM (CHDM) and neopentyl glycol with the molar ratio investment of 1.1:1 to 2.0:1
Diol compound and the dicarboxylic acid derivatives compound that is made of or mixtures thereof dimethyl terephthalate (DMT), phthalic acid
Step；
Raw material is stirred under nitrogen flowing, is carried out ester exchange reaction and esterification at 270 to 300 DEG C and is generated the step of monomer
Suddenly；And
Using nitrogen pressure, the monomer of the generation is transferred, the step of condensation polymerization is carried out at 0.01 to 1.0 support and 290 to 310 DEG C
Suddenly,
On the basis of dicarboxylic acid derivatives compound molal quantity, the diol compound includes 2 to 10 moles of % of neopentyl glycol.
2. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 1, which is characterized in that
Exquisite phthalic acid is used as the dimethyl terephthalate (DMT) and the phthalic acid.
3. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to requiring 1 or 2, which is characterized in that
It is additional to use the glycol selected from one or more of ethylene glycol, 1,3-PD and 1,4-butanediol as diol compound
Compound,
On the basis of the molal quantity of whole diol compound, the content of the additional diol compound used is 10 moles of % or less.
4. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 1 or 2, feature exist
In on the basis of the molal quantity of the dicarboxylic acid derivatives compound, also comprising 0.1 to 1.0 mole of % of isophathalic acid, realization esterification
Reaction or ester exchange reaction and condensation polymerization reaction.
5. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 1 or 2, feature exist
In,
Further include the steps that putting into catalyst,
The catalyst is selected from by titanium oxide, tetraethyl titanate, four n-propyl of metatitanic acid, tetraisopropyl titanate, the positive fourth of metatitanic acid four
Ester, tetrabutyl titanate, metatitanic acid butyl isopropyl ester, Dibutyltin oxide, manganese acetate, cobalt acetate, calcium acetate and zinc acetate composition
One or more of group.
6. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 1 or 2, feature exist
In,
Further include the steps that putting into oxidation stabilizers,
The oxidation stabilizers are selected from by trimethyl phosphate, triethyl phosphate, two aryloxy group triguaiacyl phosphate of neopentyl, three
One or more of phenyl phosphate ester, phosphonoacetate, phosphoric acid or group of phosphorous acid composition.
7. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 1 or 2, feature exist
In that adds 2 to 10 moles of % in the dicarboxylic acid derivatives compound is selected from isophathalic acid, 2,6 dicarboxylic acids of naphthalene and dimethyl
One or more of isophathalic acid and use.
8. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 5, which is characterized in that
The catalyst includes Titanium series catalyst, is synthesized comprising the catalyst 10 to 100ppm in whole input amount.
9. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 6, which is characterized in that
It is synthesized comprising the oxidation stabilizers 70 to 500ppm in whole input amount.
10. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 1 or 2, feature
It is, the intrinsic viscosity of polycyclohexylene's diformazan alcohol ester resin is 0.4 to 1.2dl/g.
11. the preparation method of polycyclohexylene's diformazan alcohol ester resin according to claim 10, feature exist
In, polycyclohexylene's diformazan alcohol ester resin include as UTM value 38 to 40.2mps intensity, 200 to
220% elongation percentage and 247 to 252mps spring rate.
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| KR20240123929A (en) | 2023-02-08 | 2024-08-16 | 에스케이마이크로웍스 주식회사 | Polyester film and plate heater comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101334598A (en) * | 2002-12-20 | 2008-12-31 | 三菱丽阳株式会社 | Polyester resin composition for toner and toner |
| CN103665351A (en) * | 2013-11-29 | 2014-03-26 | 金发科技股份有限公司 | Poly-terephthalic acid cyclohexanedimethanol /butanediol copolyester, and preparation and application thereof |
| CN104640905A (en) * | 2012-09-24 | 2015-05-20 | Sk化学株式会社 | Method for producing polycyclohexylenedimethylene terephthalate resin having excellent coloring property and polycyclohexylenedimethylene terephthalate resin produced thereby |
| US20160222157A1 (en) * | 2009-09-14 | 2016-08-04 | Sk Chemicals Co., Ltd. | Polyester resin and method for preparing the same |
-
2017
- 2017-09-05 KR KR1020170113229A patent/KR101911385B1/en active IP Right Grant
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- 2018-09-05 CN CN201811030182.1A patent/CN109456467A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101334598A (en) * | 2002-12-20 | 2008-12-31 | 三菱丽阳株式会社 | Polyester resin composition for toner and toner |
| US20160222157A1 (en) * | 2009-09-14 | 2016-08-04 | Sk Chemicals Co., Ltd. | Polyester resin and method for preparing the same |
| CN104640905A (en) * | 2012-09-24 | 2015-05-20 | Sk化学株式会社 | Method for producing polycyclohexylenedimethylene terephthalate resin having excellent coloring property and polycyclohexylenedimethylene terephthalate resin produced thereby |
| CN103665351A (en) * | 2013-11-29 | 2014-03-26 | 金发科技股份有限公司 | Poly-terephthalic acid cyclohexanedimethanol /butanediol copolyester, and preparation and application thereof |
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