CN108715633A - A kind of hydrolysis-resistant polyester and preparation method thereof - Google Patents
A kind of hydrolysis-resistant polyester and preparation method thereof Download PDFInfo
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- CN108715633A CN108715633A CN201810554335.6A CN201810554335A CN108715633A CN 108715633 A CN108715633 A CN 108715633A CN 201810554335 A CN201810554335 A CN 201810554335A CN 108715633 A CN108715633 A CN 108715633A
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- hydrolysis
- resistant polyester
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- aromatic
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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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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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 hydrolysis-resistant polyester and preparation method thereof, its end carboxyl group content≤10mol/t；And it contains general formula and isChemical structural units, in formula, Ar is the aromatic radical or its deriveding group that carbon atom number is 6~18.It is by controlling end carboxyl group content≤10mol/t and forming general formula
Description
Technical field
The invention belongs to polymeric material fields, are related to a kind of polyester, and in particular to a kind of hydrolysis-resistant polyester and its preparation
Method.
Background technology
Polyester, especially polyethylene terephthalate are had excellent performance in machinery, mechanics, chemistry etc., are had resistance to
The features such as heat, chemical-resistant reagent, mechanical strength are good, the transparency is good, is widely used in various fields.
Extend in article currently, polyester material is widely used in various high molecular orientations, such as fiber, film etc.
In product.Usually under arid and hot environment, the anti-hydrolytic performance of polyester is splendid.But polyester but easily occurs under wet heat condition
Hydrolytic cleavage, this is because polyester end group contains carboxyl, polyester is easily by the end of its remaining under conditions of hot humid
End carboxyl is catalyzed and hydrolyzes, ester linkage breaking, low so as to cause its machinery, mechanics, chemical characteristic；That is such material hydrolytic resistance
Difference cannot use outdoors for a long time.There are mainly three types of the methods for improving anti-hydrolytic performance：(1) coating is formed in surface of polyester；
(2) by polyester macromolecule high viscosity；(3) most commonly used to be to polyester progress end blockade to reduce end carboxyl group content
The method of end blockade.It is disclosed polyester application No. is the Chinese invention patent of CN1312327A and contains epoxy and amino official
Macromolecule end-capping reagent can be rolled into a ball and obtained after terminal carboxyl group block is reacted hydrolysis-resistant polyester by melting to heat, but the end-capping reagent
Preparation process it is complicated, production efficiency is not high；United States Patent (USP) US3193522 discloses addition carbonization dimethyleneimine or poly- carbonization two
Imines improves the hydrolytic resistance of polyester, but such compound has toxicity and expensive, it is difficult to and it is a large amount of to use, to improving
The effect of polyester hydrolytic stability is limited.
Invention content
A kind of hydrolysis-resistant polyester is provided the invention aims to overcome the deficiencies in the prior art.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is：A kind of hydrolysis-resistant polyester, its end
Carboxyl-content≤10mol/t；And it contains general formula and isChemical structural units, in formula, Ar be carbon atom number be 6~
18 aromatic radical or its deriveding group.
Optimally, it is by aromatic binary carboxylic acid or derivatives thereof and aliphatic dihydroxy alcohol by carrying out esterification, with
Polycondensation reaction is carried out with corresponding aromatic oligomer afterwards to be made.
Further, the chemical structural units are that ArCOOH is added when carrying out polycondensation reaction to carry out esterification or transesterification
Reaction obtains.
Further, the content of the Ar is calculated as the corresponding list of described aromatic binary carboxylic acid or derivatives thereof with benzene ring units
0.1~1.0mol% of member.
Optimally, the chemical shift of the Ar nucleus magnetic hydrogen spectrums is 7.5~8.0.
Further, the Ar is phenyl.
Optimally, its inherent viscosity is 0.5~1.0dl/g.
Another object of the present invention is to provide a kind of preparation method of above-mentioned hydrolysis-resistant polyester, it includes the following steps：
(a) aliphatic dihydroxy alcohol is made to carry out ester under the action of the first catalyst with aromatic binary carboxylic acid derivative
Exchange reaction obtains aromatic oligomer；
(b) described aromatic binary carboxylic acid or derivatives thereof is made to carry out esterification with the aliphatic dihydroxy alcohol, then
The aromatic oligomer is added and carries out polycondensation reaction, adds ArCOOH and carries out esterification or ester under the action of the second catalyst
Exchange reaction.
Optimally, first catalyst is the one kind being hydrated in cobalt salt, and second catalyst is in antimony class catalyst
One kind.Further, first catalyst is four hydration cobalt acetates, and second catalyst is antimony oxide
The advantageous effect that the present invention is brought is：Hydrolysis-resistant polyester of the present invention, by controlling end carboxyl group content≤10mol/t
And it forms general formula and isChemical structural units, can effectively improve the anti-hydrolytic performance of polyester in this way, and cost compared with
Low, simple for process and hydrolytic stability is good.
Specific implementation mode
Hydrolysis-resistant polyester of the present invention, its end carboxyl group content≤10mol/t；And it contains general formula and isChange
Structural unit is learned, in formula, Ar is the aromatic radical or its deriveding group that carbon atom number is 6~18.By controlling end carboxyl group content
≤ 10mol/t simultaneously forms general formula and isChemical structural units, the anti-hydrolytic performance of polyester can be effectively improved in this way,
And cost is relatively low, simple for process and hydrolytic stability is good.
Above-mentioned hydrolysis-resistant polyester is anti-by with aliphatic dihydroxy alcohol be esterified aromatic binary carboxylic acid or derivatives thereof
It answers, then carrying out polycondensation reaction with corresponding aromatic oligomer is made.Aromatic binary carboxylic acid or derivatives thereof is without special
Restriction, specifically can be selected from one kind in terephthalic acid (TPA), M-phthalic acid and naphthalenedicarboxylic acid and its esterification derivative；Slave
The performance of tool performance, heat resistance and humidity resistance considers, is preferably selected from terephthalic acid (TPA) and naphthalenedicarboxylic acid and its esterification derives
One kind in object.Aliphatic dihydroxy alcohol also not special restriction, can be the carbon atom numbers such as ethylene glycol, propylene glycol, butanediol
For six aliphatic dihydroxy alcohols below；Mouldability, crystallinity, hydrolytic resistance from polyester etc. consideration, preferably ethylene glycol.
Above-mentioned Ar is preferably one kind in phenyl, naphthalene and xenyl, or preferably nuclear-magnetism characterization H spectrums chemical shift 7.5~
Between 8.0；Specifically it is more preferably phenyl.The content of the Ar is calculated as the aromatic binary carboxylic acid or its derivative with benzene ring units
0.1~1.0mol% of object corresponding unit；If when less than 0.1mol%, may result in the effect to reducing end carboxyl group content
Fruit unobvious；And when higher than 1.0mol%, the molecular weight of polyester can be influenced.Final hydrolysis-resistant polyester inherent viscosity obtained is preferred
For 0.5~1.0dl/g.
The preparation method of above-mentioned hydrolysis-resistant polyester, it includes the following steps：(a) make the aliphatic dihydroxy alcohol and aromatic series
Dicarboxylic acid derivatives carry out ester exchange reaction under the action of the first catalyst and obtain aromatic oligomer；(b) make the fragrance
Race's dicarboxylic acids or derivatives thereof and the aliphatic dihydroxy alcohol carry out esterification, be then added the aromatic oligomer into
Row polycondensation reaction adds ArCOOH and carries out esterification or ester exchange reaction under the action of the second catalyst.First catalysis
Agent is the one kind being hydrated in cobalt salt, can be specifically four hydration cobalt acetates etc.；Second catalyst is in antimony class catalyst
One kind can be specifically antimony oxide etc..
The preferred embodiment of the invention will be described in detail below：
Embodiment 1
The present embodiment provides a kind of hydrolysis-resistant polyesters and preparation method thereof, specifically include following steps：
(a) ethylene glycol and dimethyl terephthalate (DMT) (molar ratio 2 are added into the reactive tank of rectifying column：1) four, are added
It is hydrated cobalt acetate (as ester exchange catalyst, its additive amount is the about 500ppm in oligomer) and carries out ester friendship at 140 DEG C
It changes and reacts to obtain oligomer (i.e. diglycol terephthalate)；Then temperature in reactive tank is promoted to 250 DEG C so that generate
Methanol be constantly distillated away, with the progress of transesterification, obtain diglycol terephthalate until ester exchange reaction
Rate is about 98%；
(b) under conditions of 250 DEG C, by terephthalic acid (TPA) and ethylene glycol with 1：1.14 molar ratio, which is added, is furnished with bottom material pair
Esterification is carried out in the reaction kettle (carrying rectifying column) of phthalic acid binaryglycol ester, it is (logical that reactivity to be esterified reaches 97%
Cross the output acquisition for calculating by-product water)；It is anti-that aforementioned diglycol terephthalate oligomer obtained is transferred to this
It answers in kettle, addition after five minutes is equivalent to the benzoic acid of terephthalic acid (TPA) structural unit 1.0mol%, adds catalyst after five minutes
Antimony oxide (300ppm that poly terephthalic acid binaryglycol ester total amount is equivalent in terms of antimony element), 5 points after addition
Clock, which starts to be depressurized to 100Pa or less, is warming up to 300 DEG C continues polycondensation reaction (entire polycondensation reaction continues 2~4 hours),
To reach spue after required polymer viscosity 0.7dL/g, cooling and dicing, nuclear-magnetism characterization is shown in Table 2.
Embodiment 2
The present embodiment provides a kind of hydrolysis-resistant polyester and preparation method thereof, it with it is almost the same in embodiment 1, it is different
It is：In step (b), addition is equivalent to the benzoic acid of terephthalic acid (TPA) structural unit 0.8mol%, terephthalic acid (TPA) and ethylene glycol
Molar ratio correspondence be adjusted to 1：1.15, the additive amount of antimony oxide is 250ppm.
Embodiment 3
The present embodiment provides a kind of hydrolysis-resistant polyester and preparation method thereof, it with it is almost the same in embodiment 1, it is different
It is：In step (b), addition is equivalent to the benzoic acid of terephthalic acid (TPA) structural unit 1.0mol%, terephthalic acid (TPA) and ethylene glycol
Molar ratio correspondence be adjusted to 1：1.15, the additive amount of antimony oxide is 250ppm.
Embodiment 4
The present embodiment provides a kind of hydrolysis-resistant polyester and preparation method thereof, it with it is almost the same in embodiment 1, it is different
It is：In step (b), the molar ratio of dimethyl terephthalate (DMT) and ethylene glycol is 1：2 carry out esterification；Addition is equivalent to benzene
The additive amount of the benzoic acid of dioctyl phthalate structural unit 0.8mol%, antimony oxide is 300ppm.
Embodiment 5
The present embodiment provides a kind of hydrolysis-resistant polyester and preparation method thereof, it with it is almost the same in embodiment 1, it is different
It is：In step (b), until spuing after reaching required polymer viscosity 0.5dL/g, cooling and dicing.
Embodiment 6
The present embodiment provides a kind of hydrolysis-resistant polyester and preparation method thereof, it with it is almost the same in embodiment 1, it is different
It is：In step (b), until spuing after reaching required polymer viscosity 1.0dL/g, cooling and dicing.
Comparative example 1
This example provides a kind of polyester and preparation method thereof, it with it is almost the same in embodiment 1, the difference is that：Step (b)
In, it is not added with benzoic acid.
The raw material proportioning and performance evaluation table of product in 1 embodiment 1-6 of table, comparative example 1
Product in 2 embodiment 1-6 of table, comparative example 11The chemical shift of H spectrums and integral area table
In table 1, each English abbreviation is specially：EG, ethylene glycol；TPA, terephthalic acid (TPA)；DMT, dimethyl terephthalate (DMT)；
AO, antimony oxide.
Each test event in Tables 1 and 2 evaluation method is as follows：
(1) intrinsic viscosity (IV) of polyester raw material
Sample dissolves in facing chlorophenol, is measured at 25 DEG C using formula viscosimeter difficult to understand；
(2) the end COOH values of polyester
The use of face methylphenol is that after solvent dissolves, the standard NaOH aqueous solutions of 0.02mol/L are used under the conditions of 25 DEG C
Automatic Titration is carried out, COOH amounts are tested out；
(3) Ar- group contents (mol%)
It takes 0.05g polyester slices to be dissolved in deuterated trifluoroacetic acid solvent, is tested by 400MHz nuclear magnetic resonance, according to
Ar-'s1H spectrum signatures peak integral area S2, S3 and terephthalic acid (TPA) characteristic peak integral area S1 ratio-dependent Ar- group contents.
Calculation formula is as follows：Ar- group contents (mol%)=((S2+S3)/5)/(S1/4) * 100；
(4) anti-hydrolytic performance index △ COOH
A certain amount of polymer blend is taken to be placed in the hydrolysis processing unit of sealing, in 155 DEG C, the vapor of 0.46MPa
Under the conditions of handle 4h, then will treated that sample is placed in dries at room temperature, measure its end COOH amounts (mol/t), than
The variation of polymer blend COOH (mol/t) amounts more before and after the processing, calculates anti-hydrolytic performance △ COOH values, calculation formula △
COOH=COOHBefore processing-COOHAfter processing, △ COOH values are lower to illustrate that hydrolytic resistance is better；
(5) Heat-tolerant index △ IV
10g polymer blends are taken, after drying process (polymer blend moisture content is in 100pm or less), are put into temperature
It is heat-treated under the conditions of being 300 DEG C, is quenched polymer blend after 30min.The front and back polymer blend of test heat treatment
Inherent viscosity IV (dL/g) and calculate polymer blend heat resistance index △ IV, calculation formula △ IV=IVBefore processing-
IVAfter processing, △ IV values are lower to illustrate that heat resistance is better.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of hydrolysis-resistant polyester, it is characterised in that：Its end carboxyl group content≤10mol/t；And it contains general formula and isChemical structural units, in formula, Ar is the aromatic radical or its deriveding group that carbon atom number is 6~18.
2. hydrolysis-resistant polyester according to claim 1, it is characterised in that：It by by aromatic binary carboxylic acid or its derivative
Object carries out esterification with aliphatic dihydroxy alcohol, and then carrying out polycondensation reaction with corresponding aromatic oligomer is made.
3. hydrolysis-resistant polyester according to claim 2, it is characterised in that：The chemical structural units are anti-in progress polycondensation
The seasonable ArCOOH that is added carries out esterification or ester exchange reaction acquisition.
4. hydrolysis-resistant polyester according to claim 2, it is characterised in that：The content of the Ar is calculated as described with benzene ring units
0.1~1.0mol% of aromatic binary carboxylic acid or derivatives thereof corresponding unit.
5. hydrolysis-resistant polyester according to claim 1, it is characterised in that：The chemical shift of the Ar nucleus magnetic hydrogen spectrums is 7.5
~8.0.
6. hydrolysis-resistant polyester according to claim 5, it is characterised in that：The Ar is phenyl.
7. hydrolysis-resistant polyester according to claim 1, it is characterised in that：Its inherent viscosity is 0.5~1.0dl/g.
8. the preparation method of any hydrolysis-resistant polyester in claim 1 to 7, which is characterized in that it includes the following steps：
(a) aliphatic dihydroxy alcohol is made to carry out transesterification under the action of the first catalyst with aromatic binary carboxylic acid derivative
React to obtain aromatic oligomer；
(b) so that described aromatic binary carboxylic acid or derivatives thereof is carried out esterification with the aliphatic dihydroxy alcohol, be then added
The aromatic oligomer carries out polycondensation reaction, adds ArCOOH and carries out esterification or transesterification under the action of the second catalyst
Reaction.
9. the preparation method of hydrolysis-resistant polyester according to claim 8, it is characterised in that：First catalyst is hydration
One kind in cobalt salt, second catalyst are one kind in antimony class catalyst.
10. the preparation method of hydrolysis-resistant polyester according to claim 9, it is characterised in that：First catalyst is four
It is hydrated cobalt acetate, second catalyst is antimony oxide.
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| CN201810554335.6A CN108715633A (en) | 2018-06-01 | 2018-06-01 | A kind of hydrolysis-resistant polyester and preparation method thereof |
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| CN201810554335.6A CN108715633A (en) | 2018-06-01 | 2018-06-01 | A kind of hydrolysis-resistant polyester and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1930216A (en) * | 2004-03-09 | 2007-03-14 | 三菱化学株式会社 | Polybutylene terephthalate pellet, compounded product thereof, molded product thereof and method for producing them |
| CN101050274A (en) * | 2006-04-04 | 2007-10-10 | 东丽纤维研究所（中国）有限公司 | Method for preparing hydrolytic resisting polyester |
| CN105367766A (en) * | 2014-08-27 | 2016-03-02 | 东丽纤维研究所（中国）有限公司 | Polyester composition and preparing method and application thereof |
| CN105461905A (en) * | 2014-08-27 | 2016-04-06 | 东丽纤维研究所（中国）有限公司 | Polyester composition, and preparation method and application thereof |
| CN106832810A (en) * | 2017-01-16 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | A kind of hydrolysis-resistant polyester and preparation method thereof |
-
2018
- 2018-06-01 CN CN201810554335.6A patent/CN108715633A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1930216A (en) * | 2004-03-09 | 2007-03-14 | 三菱化学株式会社 | Polybutylene terephthalate pellet, compounded product thereof, molded product thereof and method for producing them |
| CN101050274A (en) * | 2006-04-04 | 2007-10-10 | 东丽纤维研究所（中国）有限公司 | Method for preparing hydrolytic resisting polyester |
| CN105367766A (en) * | 2014-08-27 | 2016-03-02 | 东丽纤维研究所（中国）有限公司 | Polyester composition and preparing method and application thereof |
| CN105461905A (en) * | 2014-08-27 | 2016-04-06 | 东丽纤维研究所（中国）有限公司 | Polyester composition, and preparation method and application thereof |
| CN106832810A (en) * | 2017-01-16 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | A kind of hydrolysis-resistant polyester and preparation method thereof |
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