CN107602835A - It is a kind of that the method for preparing high viscosity PBT is modified using macromolecule chain extension - Google Patents
It is a kind of that the method for preparing high viscosity PBT is modified using macromolecule chain extension Download PDFInfo
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- CN107602835A CN107602835A CN201710633754.4A CN201710633754A CN107602835A CN 107602835 A CN107602835 A CN 107602835A CN 201710633754 A CN201710633754 A CN 201710633754A CN 107602835 A CN107602835 A CN 107602835A
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- chain extension
- pbt
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- chain extender
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Abstract
The present invention relates to a kind of method for being modified using macromolecule chain extension and preparing high viscosity PBT.Chain extension is carried out to PBT from the chain extender for including the functional group with carboxyl, hydroxyl reaction.The chain extender that the present invention uses reacts with carboxyl and Hydroxyl Prepolymers, causes strand diffusion to extend, so as to realize the solidified forming of resin.In polyester processing technology, because thermal degradation and hydrolysis cause molecular mass to reduce, the increase of end carboxyl quantity, reduced so as to the mechanically and chemically performance of polymer.Difunctional micromolecular compound is added under the conditions of reactively blending, these bifunctional compounds contain the easily functional group with the reaction such as carboxyl, hydroxyl, directly it can be reacted with low molecule quality oligomer, " bridge formation " is formed between two polymer chains, dramatically increase molecular mass, the viscosity of raising system, content of carboxyl end group is reduced, therefore be to select compound and hydroxyl or carboxyl addition to polyester chain extension.
Description
Technical field
The present invention relates to a kind of method for being modified using macromolecule chain extension and preparing high viscosity PBT, belongs to PBT processing and prepares skill
Art field.
Background technology
Polybutylene terephthalate (PBT) (PBT), PBT belongs to thermoplastic polyester plastic, makes suitable for different processers
With.General optical cable needs highly viscous PBT to carry out extruder extrusion processing with PBT, is manufactured into optical fiber loose tube, traditional processing
High viscosity PBT prepares highly viscous PBT by the way of low viscosity PBT resin solid-phase tack producing, and this mode needs to be born
Pressure, reactor heating, energy consumption is big, production capacity is low, and subsequently dedusting, temperature-fall period are complex, and used device, recruitment are more.
The content of the invention
The present invention is directed to drawbacks described above, and it is an object of the present invention to provide a kind of carry out melt thickening using chemical chain extension method, has work
Skill flow is short, equipment investment is few, reaction speed is fast and it is controllable, production efficiency is high, strong applicability, it is easy to operate the advantages that one kind
The method for preparing high viscosity PBT is modified using macromolecule chain extension.
It is for this technical solution adopted by the present invention：The present invention is from the functional group included with carboxyl, hydroxyl reaction
Chain extender carries out chain extension to PBT.
The chain extender is one or both of bisoxirane, bisoxazoline mixture.
The content of the chain extender is the 0.05~1% of PBT weight.
In the chain extender, by weight：
Bisoxirane 10~45%；
Bisoxazoline 55~90%.
By the PBT that inherent viscosity is 0.8~1.2dL/g, 0.02~1% highly viscous white oil is added, is well mixed, then
0.05~1% chain extender is added, then adds 0.02~0.8% nucleator, is well mixed, is heated in melting process and expanded using extruder
The reaction of end group and chain extender is played in chain agent so that the length increase of segment.
In chain extension process, chain extension is carried out by the way of repeatedly adding：Chain extension addition bisoxazoline, a secondary expansion
Chain addition bisoxirane, the three times mixture of chain extension addition bisoxirane and bisoxazoline.
Each time addition chain extender weight be：
The bisoxazoline once added accounts for the 75~90% of bisoxazoline gross weight；
The bisoxirane of secondary addition accounts for the 75~90% of bisoxirane gross weight；
The chain extender added three times is the bisoxirane of surplus and the mixture of bisoxazoline.
It is an advantage of the invention that：The chain extender that the present invention uses reacts with carboxyl and Hydroxyl Prepolymers, causes strand to expand
Dissipate and extend, so as to realize the solidified forming of resin.In polyester processing technology, because thermal degradation and hydrolysis cause molecular mass to drop
It is low, the increase of end carboxyl quantity, reduced so as to the mechanically and chemically performance of polymer.Difunctional is added under the conditions of reactively blending
Micromolecular compound, these bifunctional compounds contain the easily functional group with the reaction such as carboxyl, hydroxyl, can directly with low point
Protonatomic mass oligomer reacts, and forms " bridge formation " between two polymer chains, dramatically increases molecular mass, improve the viscosity of system, drops
Low terminal carboxy content, therefore be to select compound and hydroxyl or carboxyl addition to polyester chain extension.
The end group of PBT resin contains carboxyl and hydroxyl, therefore selects the polyfunctional group active material that can be reacted with its end group,
Selected chain extender is required to the functional group with the reaction such as carboxyl, hydroxyl.
Present invention selection viscosity is raw material for 1.0 PBT resin, and viscosity is improved to 1.3, content of carboxyl end group from 30 from 1.0
15, color and luster b values are decreased to less than less than 3, melt flow rate (MFR):7 ~ 10g/10min, color and luster keep the whiteness of original PBT resin,
Oxidation jaundice, content of carboxyl end group caused by process heating is avoided to be greatly reduced, straight chain increases, and flow rate is substantially reduced to
In optical fiber secondary cocoon material PBT use critical field, it is adapted to extrusion packaged tube, in addition, also increased in mechanical performance,
The increment 55Mpa of yield strength 53, the increment 2600Mpa of tensile modulus of elasticity 2400, notch impact strength are improved to 6.0kj/ from 4.5
m2。
Embodiment
Embodiment 1：
The present invention carries out chain extension from the chain extender for including the functional group with carboxyl, hydroxyl reaction to PBT.
The chain extender is bisoxirane（Hydroxyl）, bisoxazoline（Carboxyl）One or both of mixture.
The content of the chain extender is the 0.52% of PBT weight.
In the chain extender, by weight：
Bisoxirane 18%；
Bisoxazoline 82%.
By the PBT that inherent viscosity is 1.0dL/g, 0.2% highly viscous white oil is added, is well mixed, then adds 0.52%
Chain extender, then 0.3% nucleator is added, it is well mixed, heats chain extender in melting process using extruder and play end group and chain extension
The reaction of agent so that the length increase of segment.
In chain extension process, chain extension is carried out by the way of repeatedly adding：Chain extension addition bisoxazoline, a secondary expansion
Chain addition bisoxirane, the three times mixture of chain extension addition bisoxirane and bisoxazoline.
Each time addition chain extender weight be：
The bisoxazoline once added accounts for the 85% of bisoxazoline gross weight；
The bisoxirane of secondary addition accounts for the 80% of bisoxirane gross weight；
The chain extender added three times is the bisoxirane of surplus and the mixture of bisoxazoline.
Embodiment 2：
The present invention carries out chain extension from the chain extender for including the functional group with carboxyl, hydroxyl reaction to PBT.
The chain extender is bisoxirane（Hydroxyl）, bisoxazoline（Carboxyl）One or both of mixture.
The content of the chain extender is the 0.2% of PBT weight.
In the chain extender, by weight：
Bisoxirane 20%；
Bisoxazoline 80%.
By the PBT that inherent viscosity is 0.8dL/g, 0.4% highly viscous white oil is added, is well mixed, then adds 0.42%
Chain extender, then 0.1% nucleator is added, it is well mixed, heats chain extender in melting process using extruder and play end group and chain extension
The reaction of agent so that the length increase of segment.
In chain extension process, chain extension is carried out by the way of repeatedly adding：Chain extension addition bisoxazoline, a secondary expansion
Chain addition bisoxirane, the three times mixture of chain extension addition bisoxirane and bisoxazoline.
Each time addition chain extender weight be：
The bisoxazoline once added accounts for the 75% of bisoxazoline gross weight；
The bisoxirane of secondary addition accounts for the 85% of bisoxirane gross weight；
The chain extender added three times is the bisoxirane of surplus and the mixture of bisoxazoline.
Embodiment 3：
The present invention carries out chain extension from the chain extender for including the functional group with carboxyl, hydroxyl reaction to PBT.
The chain extender is bisoxirane（Hydroxyl）, bisoxazoline（Carboxyl）One or both of mixture.
The content of the chain extender is the 0.058% of PBT weight.
In the chain extender, by weight：
Bisoxirane 26%；
Bisoxazoline 74%.
By the PBT that inherent viscosity is 1.1dL/g, 0.09% highly viscous white oil is added, is well mixed, then adds 0.48%
Chain extender, then 0.37% nucleator is added, it is well mixed, heats chain extender in melting process using extruder and play end group with expanding
The reaction of chain agent so that the length increase of segment.
In chain extension process, chain extension is carried out by the way of repeatedly adding：Chain extension addition bisoxazoline, a secondary expansion
Chain addition bisoxirane, the three times mixture of chain extension addition bisoxirane and bisoxazoline.
Each time addition chain extender weight be：
The bisoxazoline once added accounts for the 90% of bisoxazoline gross weight；
The bisoxirane of secondary addition accounts for the 82% of bisoxirane gross weight；
The chain extender added three times is the bisoxirane of surplus and the mixture of bisoxazoline.
The NA-10 models of organic synthesis can be selected in the nucleator of the present invention.
Because optical fiber secondary cocoon material is to HMW PBT resin, high intrinsic viscosity, and merely from PBT production work
Skill is difficult to obtain HMW PBT；Therefore its molecular weight is improved using the method being modified to PBT, wherein more effective
Method be chemical chain extension.Chemical chain extension not only improves PBT molecular weight, while can reduce PBT end carboxyl (CV) content, improves
Its hydrolytic stability.
, it is necessary to carry out the process of extruder heating melting, Ye Shiyi during downstream optical cable factory production optical fiber loose tube
Individual to be similar to modifying process, therefore, the technical program need not carry out heating melting, modified pelletizing, and scheme is to be by inherent viscosity
1.0dL/g PBT, add 0.02~1% highly viscous white oil（Bond chain extender and reach the effect of lubrication）, it is well mixed, adds
Add 0.05~1% chain extender, then add 0.02~0.8% nucleator（Reach the effect of the Loose tube lateral pressure resistant after improving output）,
Well mixed, optical cable factory is using in extruder heating melting process, and chain extender serves the reaction of end group and chain extender so that chain
The length increase of section, so as to reach the effect for improving its molecular weight, simplifies production process.
Claims (7)
1. a kind of be modified the method for preparing high viscosity PBT using macromolecule chain extension, it is characterised in that from include with carboxyl,
The chain extender of the functional group of hydroxyl reaction carries out chain extension to PBT.
2. a kind of method that preparation high viscosity PBT is modified using macromolecule chain extension according to claim 1, its feature are existed
In the chain extender is one or both of bisoxirane, bisoxazoline mixture.
3. a kind of method that preparation high viscosity PBT is modified using macromolecule chain extension according to claim 2, its feature are existed
In the content of the chain extender is the 0.05~1% of PBT weight.
4. a kind of method that preparation high viscosity PBT is modified using macromolecule chain extension according to claim 3, its feature are existed
In in the chain extender, by weight：
Bisoxirane 10~45%；
Bisoxazoline 55~90%.
5. a kind of method that preparation high viscosity PBT is modified using macromolecule chain extension according to claim 1, its feature are existed
In, by the PBT that inherent viscosity is 0.8~1.2dL/g, 0.02~1% highly viscous white oil is added, it is well mixed, then add
0.05~1% chain extender, then 0.02~0.8% nucleator is added, it is well mixed, chain extender in melting process is heated using extruder
Play the reaction of end group and chain extender so that the length increase of segment.
6. a kind of method that preparation high viscosity PBT is modified using macromolecule chain extension according to claim 5, its feature are existed
In in chain extension process, chain extension is carried out by the way of repeatedly adding：One time chain extension addition bisoxazoline, secondary chain extension add
Add bisoxirane, the three times mixture of chain extension addition bisoxirane and bisoxazoline.
7. a kind of method that preparation high viscosity PBT is modified using macromolecule chain extension according to claim 6, its feature are existed
In the weight of each addition chain extender is：
The bisoxazoline once added accounts for the 75~90% of bisoxazoline gross weight；
The bisoxirane of secondary addition accounts for the 75~90% of bisoxirane gross weight；
The chain extender added three times is the bisoxirane of surplus and the mixture of bisoxazoline.
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| CN201710633754.4A CN107602835A (en) | 2017-07-28 | 2017-07-28 | It is a kind of that the method for preparing high viscosity PBT is modified using macromolecule chain extension |
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| CN201710633754.4A CN107602835A (en) | 2017-07-28 | 2017-07-28 | It is a kind of that the method for preparing high viscosity PBT is modified using macromolecule chain extension |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110219175A (en) * | 2019-06-04 | 2019-09-10 | 海安腾昱智能科技有限公司 | Fibrous elasticity body after polymerization technique |
| CN111154240A (en) * | 2020-01-20 | 2020-05-15 | 湖北工业大学 | Modification method of high-performance and hydrolysis-resistant polybutylene terephthalate resin for optical cable sheath |
| CN112724391A (en) * | 2020-12-14 | 2021-04-30 | 新疆蓝山屯河高端新材料工程技术研究中心(有限公司) | Application of chain extender in improving viscosity of polyester compound, modified polyester compound and preparation method thereof |
| CN114921065A (en) * | 2022-03-18 | 2022-08-19 | 上海金发科技发展有限公司 | PBT composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380355A (en) * | 2002-04-24 | 2002-11-20 | 广州金发科技股份有限公司 | Hydrolysis-resistant high-viscosity polytetramethylene terephthalate compound |
| CN101851345A (en) * | 2009-04-03 | 2010-10-06 | 上海日之升新技术发展有限公司 | Chain extension method of engineering resin and reclaimed material thereof |
| CN102850738A (en) * | 2012-09-10 | 2013-01-02 | 江苏南方通信科技有限公司 | PBT material used in optical fiber secondary coating, and preparation method and production system thereof |
-
2017
- 2017-07-28 CN CN201710633754.4A patent/CN107602835A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380355A (en) * | 2002-04-24 | 2002-11-20 | 广州金发科技股份有限公司 | Hydrolysis-resistant high-viscosity polytetramethylene terephthalate compound |
| CN101851345A (en) * | 2009-04-03 | 2010-10-06 | 上海日之升新技术发展有限公司 | Chain extension method of engineering resin and reclaimed material thereof |
| CN102850738A (en) * | 2012-09-10 | 2013-01-02 | 江苏南方通信科技有限公司 | PBT material used in optical fiber secondary coating, and preparation method and production system thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王小君等: "扩链剂ADR4370S对聚对苯二甲酸丁二醇酯的动态流变行为及力学性能的影响", 《高分子材料科学与工程》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110219175A (en) * | 2019-06-04 | 2019-09-10 | 海安腾昱智能科技有限公司 | Fibrous elasticity body after polymerization technique |
| CN111154240A (en) * | 2020-01-20 | 2020-05-15 | 湖北工业大学 | Modification method of high-performance and hydrolysis-resistant polybutylene terephthalate resin for optical cable sheath |
| CN111154240B (en) * | 2020-01-20 | 2022-02-01 | 湖北工业大学 | Modification method of high-performance and hydrolysis-resistant polybutylene terephthalate resin for optical cable sheath |
| CN112724391A (en) * | 2020-12-14 | 2021-04-30 | 新疆蓝山屯河高端新材料工程技术研究中心(有限公司) | Application of chain extender in improving viscosity of polyester compound, modified polyester compound and preparation method thereof |
| CN114921065A (en) * | 2022-03-18 | 2022-08-19 | 上海金发科技发展有限公司 | PBT composite material and preparation method and application thereof |
| CN114921065B (en) * | 2022-03-18 | 2024-03-19 | 上海金发科技发展有限公司 | PBT composite material and preparation method and application thereof |
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Application publication date: 20180119 |