CN108752576A - A kind of preparation method of thickening PBT slices for optical cable - Google Patents
A kind of preparation method of thickening PBT slices for optical cable Download PDFInfo
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- CN108752576A CN108752576A CN201810665205.XA CN201810665205A CN108752576A CN 108752576 A CN108752576 A CN 108752576A CN 201810665205 A CN201810665205 A CN 201810665205A CN 108752576 A CN108752576 A CN 108752576A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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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
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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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation methods of the thickening PBT slices for optical cable.It is characterized in that：The preparation method is to use p-phthalic acid and 1, PBT slices are made by esterification, prepolymerization reaction and final polycondensation reaction in 4- butanediols, dual-component catalyst is used in the synthesis technology of PBT, the dual-component catalyst is ethyl acetoacetate-isopropyl titanate chelate and nano-titanium dioxide, and the molar ratio of the two is 1:0.9~1.1, first dual-component catalyst is dissolved in 1,4-butanediol, prewired solution is made, is then divided to two sections to be added in reaction kettle of the esterification and prepolymerization reaction kettle prewired solution and reacts；Steric hindrance aromatic monomer carbodiimides is added in the final polycondensation reaction stage in Last-polycondensatioreactor reactor, synthesizes polybutylene terephthalate (PBT).Side reaction of the present invention is less, and esterification yield is abundant, and the small molecules such as by-product THF are less, and the thickening time can shorten the time 20%~30%, and product quality is more stable.
Description
Technical field
The present invention relates to a kind of preparation methods of PBT slices, and in particular to a kind of system of thickening PBT slices for optical cable
Preparation Method.
Background technology
The main material that optical cable makes optical fiber bundle tubes with PBT material is PBT, and full name is polybutylene terephthalate (PBT),
It is last one of barrier to fiber optic protection in optical cable manufacturing procedure, since optical cable requires excellent resistance to side pressure with PBT
Can, so requiring the inherent viscosity of PBT very high.The method of PBT thickeninies mainly has reaction chain extension, solid-phase tack producing and directly closes
At reaction principle is shown below：Small molecule PBT+ small molecule PBT+ macromoleculars PBT+H2O；Different thickening methods are produced
PBT performances also make a world of difference, the PBT that good technique productions go out have inherent viscosity consistency is good, bending modulus is higher, beam tube
The features such as retraction is smaller and mechanical strength is stronger.
In the synthesis technology of polybutylene terephthalate (PBT), using p-phthalic acid and 1,4-butanediol through over-churning
Reaction, prepolymerization reaction and final polycondensation reaction are made.It generally uses butyl titanate as catalyst, there is catalysis effect well
Fruit, it is directly added into Esterification Stage, and addition is few, measuring difficulties, in Esterification Stage facile hydrolysis, device fouling, operation week
Phase is short, but its final slice crystallinity is high, and water content is higher in slice, is unfavorable for PBT slice thickeninies and is used for cable material.In order to
So that product viscosity reaches optical cable grade, need to carry out tackified finish, when being sliced secondary operation thickening, using solid-phase tack producing side
Formula, in crystallization temperature hereinafter, macromolecular chain cannot move in being sliced at this time, activity is happened at without fixed for reaction temperature control
Shape region, thickening mainly deviate from the small molecules such as tetrahydrofuran (THF) and water in the process, and the crystallinity such as fruit product is too high, knot
Crystalline region domain is relatively stablized, and intermolecular activity had both been unfavorable for, and is also unfavorable for the abjection of the small molecules such as water, viscosifies time lengthening, raw
Cost is produced to increase.
Invention content
The purpose of the present invention is to overcome the above shortcomings and to provide a kind of side reaction is less, small molecule is less, viscosifies the time
Short, product quality is stablized, the preparation method of the thickening PBT slices for optical cable.
The object of the present invention is achieved like this：The preparation method of a kind of thickening PBT slices for optical cable, poly- to benzene
In the synthesis technology of dioctyl phthalate butanediol ester, using dual-component catalyst, the dual-component catalyst is ethyl acetoacetate-
The mass ratio of isopropyl titanate chelate and nano-titanium dioxide, the two is 1:0.9~1.1, it is first that dual-component catalyst is molten
For solution in 175-185 DEG C of 1,4-butanediol, it is 3%~5% that the dual-component catalyst, which accounts for 1,4-butanediol mass percent,
Prewired solution is made, is then divided to two sections to be added in reaction kettle of the esterification and prepolymerization reaction kettle；Steric hindrance aromatic series is added in Last-polycondensatioreactor reactor
Monomer carbodiimides synthesizes polybutylene terephthalate (PBT).
Dual-component catalyst and prewired solution made from 1,4- butanediols are divided to the routes of two sections of additions to be respectively：One section be from
The 1,4- butanediol solutions that esterifying kettle bottom and esterifying kettle flow back after static mixer into esterifying kettle by being reacted；It is another
Section is to enter preshrunk reactor from preshrunk kettle top portion；The dual-component catalyst addition is p-phthalic acid's mass
0.05%~0.1%.
Steric hindrance aromatic monomer carbodiimides is added in final polycondensation reaction kettle.
The addition of the steric hindrance aromatic monomer carbodiimides be p-phthalic acid's mass 0.03%~
0.1%, preferably 0.05%.
The structural formula of the ethyl acetoacetate-isopropyl titanate chelate (CAS No.27858-32-8) is：
The progress meaning of the present invention is：
1, the use of dual-component catalyst ensure that reaction time of esterification, catalyst acetyl ethyl acetate-metatitanic acid isopropyl
Its hydrolysis resistance of ester chelate is poor, is added that multi-product color value is undesirable, and final products color value B values are higher, influence condition, receive
Rice titanium dioxide overcomes hydrolysis problem and product color value problem, but its reactivity is different compared with ethyl acetoacetate-metatitanic acid
Propyl ester chelate is poor, and the reaction time extends, and the utilization ratio of catalyst can be improved using dual-component catalyst.Using two-component
Catalyst so that side reaction is less in esterification, and esterification yield is abundant, and the small molecules such as by-product THF are less.Be conducive to viscosify
The abjection of journey small molecular.
2, selection is in two sections of addition catalyst of esterification and preshrunk, it is ensured that the case where Esterification Stage reaction meets condition
Under, partial reaction catalyst is added in precondensation stage, can reduce and generate water in Esterification Stage reaction to catalyst activity
It influences, also can guarantee the catalytic activity of precondensation stage catalyst.Catalyst is added in precondensation stage to cut in final product
Catalyst content in piece amorphous domain is higher, is conducive to the shortening for viscosifying the product time.During slice thickening, crystallizing
Temperature is hereinafter, macromolecular chain cannot move in being sliced at this time, and activity is happened at amorphous domain, and crystal region is very stable.
Crystalline region is free of end group and catalyst, and the catalyst content for further increasing amorphous domain is conducive to viscosify the shortening of time.
3, steric hindrance aromatic monomer carbodiimides is added in the final minification stage, meets water and acid forms stable urea derivatives
Object keeps product quality more stable to remove the water and acid in polymer, and the carbodiimides of residual in the reaction system can
It is used as chain diffusant during thickening, increases the viscosity of poly terephthalic acid.
Carbodiimides inhibits the chemical structural drawing of hydrolysis
Chemical structural drawing of the carbodiimides as chain extender
In conclusion the thickening PBT slices for optical cable prepared by the method for the present invention, side reaction is less, and esterification yield is abundant,
The small molecules such as by-product THF are less, and the thickening time can shorten the time 20%~30%, and product quality is more stable.
Specific implementation mode
Embodiment 1
Dual-component catalyst ethyl acetoacetate-isopropyl titanate chelate and nano-titanium dioxide in mass ratio 1：1 is mixed
After being heated to 180 DEG C with the prewired solution of 1,4-butanediol after conjunction, by measuring pump-metered respectively from esterifying kettle bottom and esterifying kettle
Reflux 1,4-butanediol solution after static mixer into esterifying kettle by being reacted, and from preshrunk kettle top portion to enter preshrunk anti-
It is the 0.1% of p-phthalic acid's mass to answer device, the dual-component catalyst addition.Steric hindrance is added in final polycondensation reaction kettle
Aromatic monomer carbodiimides, addition are the 0.05% of p-phthalic acid's mass.
The ethyl acetoacetate-isopropyl titanate chelate is chelated using the Tyzor-726 organic titaniums of E.I.Du Pont Company
Object.
Its PBT primary resin obtained, during downstream viscosifies, slice amorphous domain increases, and catalyst therein is residual
The more former process resin of allowance increases, and ensure that the activity of the end group in chain extension process, is easy to deviate from since it is sliced internal water, make
It is shorter to viscosify the time, can shorten the time 20%~30%.10%~15% is can save energy, energy consumption is reduced.
Embodiment 2
Dual-component catalyst ethyl acetoacetate-isopropyl titanate chelate and nano-titanium dioxide in mass ratio 1：0.9
After mixing, after being heated to 175 DEG C with the prewired solution of 1,4-butanediol, by measuring pump-metered respectively from esterifying kettle bottom and esterification
Kettle reflux 1,4-butanediol solution enters preshrunk by being reacted into esterifying kettle after static mixer, and from preshrunk kettle top portion
Reactor, the dual-component catalyst addition are the 0.05% of p-phthalic acid's mass.It is added in final polycondensation reaction kettle
Steric hindrance aromatic monomer carbodiimides, addition are the 0.03% of p-phthalic acid's mass.
Its PBT primary resin obtained can shorten the thickening time 20%~30% during downstream viscosifies.
Embodiment 3
Dual-component catalyst ethyl acetoacetate-isopropyl titanate chelate and nano-titanium dioxide in mass ratio 1：1.1
After mixing, after being heated to 185 DEG C with the prewired solution of 1,4-butanediol, by measuring pump-metered respectively from esterifying kettle bottom and esterification
Kettle reflux 1,4-butanediol solution enters preshrunk by being reacted into esterifying kettle after static mixer, and from preshrunk kettle top portion
Reactor, the dual-component catalyst addition are the 0.10% of p-phthalic acid's mass.It is added in final polycondensation reaction kettle
Steric hindrance aromatic monomer carbodiimides, addition are the 0.10% of p-phthalic acid's mass.
Its PBT primary resin obtained can shorten the thickening time 20%~30% during downstream viscosifies.
Claims (6)
1. a kind of preparation method of thickening PBT slices for optical cable, it is characterised in that：The preparation method is using essence to benzene
PBT slices are made by esterification, prepolymerization reaction and final polycondensation reaction in dioctyl phthalate and 1,4-butanediol, in the synthesis of PBT
It is ethyl acetoacetate-isopropyl titanate chelate and nanometer that dual-component catalyst, the dual-component catalyst are used in technique
The molar ratio of titanium dioxide, the two is 1:0.9~1.1, first dual-component catalyst is dissolved in 1,4-butanediol, is made pre-
With solution, then it is divided to two sections to be added in reaction kettle of the esterification and prepolymerization reaction kettle prewired solution and reacts；Final polycondensation reaction rank
Steric hindrance aromatic monomer carbodiimides is added in section in Last-polycondensatioreactor reactor, synthesizes polybutylene terephthalate (PBT), the steric hindrance virtue
The addition of fragrant race's monomer carbodiimides is the 0.03%~0.1% of p-phthalic acid's mass.
2. a kind of preparation method of thickening PBT slices for optical cable according to claim 1, it is characterised in that：It is described
Dual-component catalyst and prewired solution made from 1,4- butanediols are divided to the routes of two sections of additions to be respectively：One section is from esterifying kettle bottom
The 1,4- butanediol solutions that portion and esterifying kettle flow back after static mixer into esterifying kettle by being reacted；Another section is from pre-
Contracting kettle top portion enters preshrunk reactor.
3. a kind of preparation method of thickening PBT slices for optical cable according to claim 1, it is characterised in that：It is described
It is that dual-component catalyst is dissolved in 175-185 DEG C of 1,4-butanediol when prewired solution is prepared.
4. a kind of preparation method of thickening PBT slices for optical cable according to claim 3, it is characterised in that：It is described
It is 3%~5% that dual-component catalyst, which accounts for 1,4- butanediol mass percents,.
5. a kind of preparation method of thickening PBT slices for optical cable according to claim 1, it is characterised in that：It is described
0.05%~0.1% that total amount is p-phthalic acid's mass is added in dual-component catalyst.
6. a kind of preparation method of thickening PBT slices for optical cable according to claim 1, it is characterised in that：It is described
The addition of steric hindrance aromatic monomer carbodiimides is the 0.05% of p-phthalic acid's mass.
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| CN201810665205.XA CN108752576A (en) | 2018-06-26 | 2018-06-26 | A kind of preparation method of thickening PBT slices for optical cable |
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| CN201810665205.XA CN108752576A (en) | 2018-06-26 | 2018-06-26 | A kind of preparation method of thickening PBT slices for optical cable |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105557A (en) * | 2019-06-10 | 2019-08-09 | 河南开祥精细化工有限公司 | The adding method of polybutylene terephthalate (PBT) polyplant and catalyst |
-
2018
- 2018-06-26 CN CN201810665205.XA patent/CN108752576A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105557A (en) * | 2019-06-10 | 2019-08-09 | 河南开祥精细化工有限公司 | The adding method of polybutylene terephthalate (PBT) polyplant and catalyst |
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Application publication date: 20181106 |