CN109553761A - A kind of preparation method of PET modified unsaturated polyester resin - Google Patents
A kind of preparation method of PET modified unsaturated polyester resin Download PDFInfo
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- CN109553761A CN109553761A CN201811347259.8A CN201811347259A CN109553761A CN 109553761 A CN109553761 A CN 109553761A CN 201811347259 A CN201811347259 A CN 201811347259A CN 109553761 A CN109553761 A CN 109553761A
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- unsaturated polyester
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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
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Abstract
The invention discloses a kind of preparation methods of PET modified unsaturated polyester resin, the following steps are included: glycerol, higher boiling dihydric alcohol, useless PET and catalyst are added in reaction kettle step (1), stirring, and be rapidly heated to 220 DEG C of progress insulation reactions, give up the subsequent continuation of insurance temperature 1-2h of PET whole alcoholysis；Heat preservation terminates, and is cooled to 150 DEG C or less；Unsaturated dicarboxylic acid anhydride, monohydric alcohol and low boiling point dihydric alcohol is added in step (2), it is warming up to 150-155 DEG C, insulation reaction 0.5h, it is gradually warming up to 195-205 DEG C of progress isothermal reaction again, when water yield reaches the 85-90% of theoretical value, it vacuumizes and moisture is discharged, reaction carries out being lower than 30mgKOH/g to acid value；Step (3) is cooled to 155-160 DEG C, and polymerization inhibitor is added, is diluted using styrene, cooling, filtering.The resin and styrene-compatible of this method preparation are good, and entire technological reaction process is steadily controllable, and gained color of resin is shallow, and toughness and physical strength are preferable after resin solidification；This method raw material sources are extensive, reduce environmental pollution, and reduce production cost.
Description
Technical field
The present invention relates to resin technology field, in particular to a kind of preparation method of PET modified unsaturated polyester resin.
Background technique
With the continuous growth of PET yield and consumption figure, the amount of waste PET also constantly increases, and discarded PET has become ring
The big problem of border pollution.Countries in the world have all started to pay attention to the recycling and reproduction operation of plastics at present, and many countries have set up specially
The recovery plant of door even research institution.Unsaturated polyester resin is produced using useless PET as raw material, not only makes unsaturated polyester resin
Cost reduce, and recycle waste material, reduce environmental pollution simultaneously, " useless " can be become as " treasured ".
Generally there are following methods using useless PET synthesis unsaturated polyester resin both at home and abroad at present: (1) with the direct alcohol of dihydric alcohol
It solves useless PET and synthesizes unsaturated polyester resin；(2) synthesis polyester is reacted with binary acid after using dihydric alcohol alcoholysis, then in polyester molecule
Middle introducing dicyclopentadiene (DCPD) molecule；(3) part dihydric alcohol alcoholysis PET is replaced with polyalcohol (glycerol).Above method lacks
Point is as follows: the polyester of manufacture and the intermiscibility of styrene are poor, phenomenon of phase separation easily occur, if further improving intermiscibility, cause
Production cost is higher；DCPD molecule is introduced, technology controlling and process is complicated, and final color of resin is deeper；Glycerol is trihydroxylic alcohol containing two primary
Hydroxyl and a secondary hydroxyl can generate network molecular structure in synthesis PET Process, and reaction is not easy to control, be also easy to produce gel,
Product quality is caused to decline；If later period benzoic acid or dicyclopentadiene block polyester, the hair of gel can be effectively prevent
It is raw, but disadvantage is also apparent from: it is blocked using dicyclopentadiene, control process is more complicated, and the color for obtaining resin is deeper；Using
Benzoic acid sealing end, since distillation easily causes condensing unit to block to benzoic acid rapidly at 100 DEG C, waste water post-processing is difficult.
Summary of the invention
The present invention provides a kind of preparation method of PET modified unsaturated polyester resin, solves resin and benzene in the prior art
Ethylene poor compatibility, technology controlling and process is complicated, and processing cost is high, and gained resin appearance, quality are difficult to the problem of ensureing.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is as follows: a kind of system of PET modified unsaturated polyester resin
Preparation Method, comprising the following steps:
Glycerol, higher boiling dihydric alcohol, useless PET and catalyst are added in reaction kettle step (1), stirring, and are rapidly heated
To 220 DEG C of progress insulation reactions, give up the subsequent continuation of insurance temperature 1-2h of PET whole alcoholysis；Heat preservation terminates, and is cooled to 150 DEG C or less；
Unsaturated dicarboxylic acid anhydride, monohydric alcohol and low boiling point dihydric alcohol is added in step (2), is warming up to 150-155 DEG C, heat preservation is anti-
0.5h is answered, then is gradually warming up to 195-205 DEG C of progress isothermal reaction and is vacuumized when water yield reaches the 85-90% of theoretical value
Moisture is discharged, reaction carries out being lower than 30mgKOH/g to acid value；
Step (3) is cooled to 155-160 DEG C, and polymerization inhibitor is added, is diluted using styrene, cooling, filtering.
As a preferred embodiment, the boiling point of higher boiling dihydric alcohol described in step (1) is higher than 220 DEG C.
As a preferred embodiment, the speed of stirring described in step (1) is 300r/min.
As a preferred embodiment, insulation reaction described in step (1) carries out under nitrogen protection.
As a preferred embodiment, the boiling point of low boiling point dihydric alcohol described in step (2) is lower than 210 DEG C.
As a preferred embodiment, the dosage of each reactant is as follows:
The weight ratio of the useless PET and the dihydric alcohol is 1:0.7-1:1.2；
The weight ratio of the useless PET and the glycerol is 1:0.3-1:0.8；
The weight ratio of the useless PET and the unsaturated dicarboxylic acid anhydride is 1:0.8-1:1.4；
The molar ratio of the monohydric alcohol and the glycerol is 1:0.9-1:1.2；
The molar ratio of total carboxylic acid and total polyalcohol is 1:0.9-1:1.05；
The additional amount of the catalyst is that the useless PET weight is 0.3%；
The additional amount of the styrene is unsaturated polyester resin total weight 35%.
By adopting the above technical scheme, monohydric alcohol reacted with dibasic acid anhydride generate Monomethyl diester, Monomethyl diester again with glycerol into
Row end capping reaction, the shortcomings that effectivelying prevent gel, the prior art is overcome to block；The resin and styrene phase of this method preparation
Capacitive is good, and entire technological reaction process is steadily controllable, and gained color of resin is shallow, and toughness and physical strength are preferable after resin solidification；
This method raw material sources are extensive, reduce environmental pollution, and reduce production cost.
Specific embodiment
Specific embodiments of the present invention will be further explained below.It should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, invention described below
Technical characteristic involved in each embodiment can be combined with each other as long as they do not conflict with each other.
A kind of preparation method of PET modified unsaturated polyester resin, comprising the following steps:
Glycerol, higher boiling dihydric alcohol, useless PET and catalyst are added in reaction kettle step (1), stirring, and are rapidly heated
To 220 DEG C of progress insulation reactions, give up the subsequent continuation of insurance temperature 1-2h of PET whole alcoholysis；Heat preservation terminates, and is cooled to 150 DEG C or less；
Unsaturated dicarboxylic acid anhydride, monohydric alcohol and low boiling point dihydric alcohol is added in step (2), is warming up to 150-155 DEG C, heat preservation is anti-
0.5h is answered, then is gradually warming up to 195-205 DEG C of progress isothermal reaction and is vacuumized when water yield reaches the 85-90% of theoretical value
Moisture is discharged, reaction carries out being lower than 30mgKOH/g to acid value；
Step (3) is cooled to 155-160 DEG C, and polymerization inhibitor is added, is diluted using styrene, cooling, filtering.
As a preferred embodiment, the boiling point of higher boiling dihydric alcohol is higher than 220 DEG C in step (1).
As a preferred embodiment, the speed stirred in step (1) is 300r/min.
As a preferred embodiment, insulation reaction carries out under nitrogen protection in step (1).
As a preferred embodiment, the boiling point of low boiling point dihydric alcohol is lower than 210 DEG C in step (2).
As a preferred embodiment, the dosage of each reactant is as follows:
The weight ratio of useless PET and dihydric alcohol is 1:0.7-1:1.2；
The weight ratio of useless PET and glycerol is 1:0.3-1:0.8；
The weight ratio of useless PET and unsaturated dicarboxylic acid anhydride is 1:0.8-1:1.4；
The molar ratio of monohydric alcohol and glycerol is 1:0.9-1:1.2；
The molar ratio of total carboxylic acid and total polyalcohol is 1:0.9-1:1.05；
The additional amount of catalyst is that useless PET weight is 0.3%；
The additional amount of styrene is unsaturated polyester resin total weight 35%.
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that in following embodiment: using
Useless PET is from the poly terephthalic acid recycled in polyester production process and in daily use as one of raw material
Glycol ester (PET)；By taking maleic anhydride as an example, dihydric alcohol simultaneously not only limits dibasic acid anhydride by taking diethylene glycol (DEG), propylene glycol as an example
In this, it may also include ethylene glycol, a contracting propylene glycol, 2- methyl-1, one of 3-propanediol, neopentyl glycol or a variety of；One
First alcohol is by taking isooctanol as an example, it is not limited to this, may also include one of ethyl alcohol, isopropanol, cyclohexanol or a variety of；It urges
Agent by taking zinc acetate as an example, it is not limited to this；Polymerization inhibitor by taking adjacent methyl hydroquinone as an example, it is not limited to this.
Embodiment 1
In a 2L four-hole boiling flask with thermometer, mechanical agitator, nitrogen ingress pipe and reflux condenser, successively
95g glycerol (technical grade, purity 95%wt), 270g diethylene glycol (DEG), the useless PET and 1g zinc acetate of 380g is added, opens mechanical stirring,
It is stirred, is rapidly heated under nitrogen protection to 220 DEG C of progress insulation reactions with the speed of 260r/min, when useless PET is whole
The subsequent continuation of insurance temperature 1h of alcoholysis, reaction kettle cooling.
Temperature is reduced to 150 DEG C hereinafter, 360g maleic anhydride and 76g propylene glycol is added, and it is anti-to be warming up to 150 DEG C of heat preservations
0.5h is answered, then is gradually warming up to 195 DEG C of progress isothermal reactions, notices that control evaporates a temperature, until acid value reaches 55mgKOH/g, to
It when water yield reaches the 85-90% of theoretical amount, vacuumizes and moisture is forced to be discharged, carry out reaction to acid value lower than 25mgKOH/g.
155 DEG C of addition 0.3g neighbour's methyl hydroquinones are cooled to, are cooled to 120 DEG C after mixing evenly, 770g benzene second is added
Alkene dilution, cooling are filtered up to unsaturated polyester resin finished product.
Embodiment 2
In a 2L four-hole boiling flask with thermometer, mechanical agitator, nitrogen ingress pipe and reflux condenser, successively
60g glycerol (technical grade, purity 95%wt), 380g diethylene glycol (DEG), the useless PET and 1g zinc acetate of 380g is added, opens mechanical stirring,
It is stirred, is rapidly heated under nitrogen protection to 220 DEG C of progress insulation reactions with the speed of 250r/min, when useless PET is whole
The subsequent continuation of insurance temperature 2h of alcoholysis, reaction kettle cooling.
Temperature is reduced to 150 DEG C hereinafter, 450g maleic anhydride, 78g isooctanol and 45g propylene glycol is added, and is warming up to
155 DEG C of insulation reaction 0.5h, then 200 DEG C of progress isothermal reactions are gradually warming up to, notice that control evaporates a temperature, until acid value reaches
55mgKOH/g is vacuumized and moisture is forced to be discharged when water yield reaches the 85-90% of theoretical amount, carries out reaction low to acid value
In 25mgKOH/g.
160 DEG C of addition 0.3g neighbour's methyl hydroquinones are cooled to, are cooled to 120 DEG C after mixing evenly, 765g benzene second is added
Alkene dilution, cold filtration is up to unsaturated polyester resin finished product.
Comparative experiments and result:
Note: gelling time test method: 25 DEG C of water-baths, 100 grams of resin+1ml isooctyl acids bore (1%)+2ml peroxidating first and second
Ketone.
By the above experimental result as it can be seen that the unsaturated polyester (UP) and styrene that are synthesized in embodiment 1-2 using the method for the present invention
Compatibility it is good, solve the problems, such as that the unsaturated polyester (UP) of alcoholysis PET synthesis and styrene-compatible are poor, while keeping entire technique anti-
Answer process steadily controllable, gained color of resin is shallow, economic and environment-friendly.Have after resin solidification obtained by method of the invention good
Toughness and physical strength, while overcoming the disadvantage of polyester Yu styrene dissolubility difference, and raw material sources are extensive, have and subtract
The advantages that few environmental pollution, reduction production cost.
The effect of monohydric alcohol be with maleic acid anhydride reactant generate maleic acid monoester, maleic acid monoester again with
Glycerol carries out end capping reaction, effectively prevent gel, thus the shortcomings that overcoming prior art sealing end, and in this way
The unsaturated polyester (UP) of synthesis and the compatibility of styrene are good, solve the unsaturated polyester (UP) and styrene-compatible of alcoholysis PET synthesis
The problem of difference, while keeping entire technological reaction process steadily controllable, gained color of resin is shallow, economic and environment-friendly；Tree obtained by this method
There is good toughness and physical strength after rouge solidification, and raw material sources are extensive, has and reduce environmental pollution, reduction is produced into
This advantages that.
Above the embodiments of the present invention are described in detail, but the present invention is not limited to described embodiments.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out more
Kind change, modification, replacement and modification, still fall in protection scope of the present invention.
Claims (6)
1. a kind of preparation method of PET modified unsaturated polyester resin, which comprises the following steps:
Glycerol, higher boiling dihydric alcohol, useless PET and catalyst are added in reaction kettle step (1), stirring, and are rapidly heated to 220
DEG C carry out insulation reaction, give up the subsequent continuation of insurance temperature 1-2h of PET whole alcoholysis；Heat preservation terminates, and is cooled to 150 DEG C or less；
Unsaturated dicarboxylic acid anhydride, monohydric alcohol and low boiling point dihydric alcohol is added in step (2), is warming up to 150-155 DEG C, insulation reaction
0.5h, then be gradually warming up to 195-205 DEG C of progress isothermal reaction, when water yield reaches the 85-90% of theoretical value, vacuumize by
Moisture discharge, reaction carry out being lower than 30mgKOH/g to acid value；
Step (3) is cooled to 155-160 DEG C, and polymerization inhibitor is added, is diluted using styrene, cooling, filtering.
2. the preparation method of PET modified unsaturated polyester resin according to claim 1, it is characterised in that: institute in step (1)
The boiling point for stating higher boiling dihydric alcohol is higher than 220 DEG C.
3. the preparation method of PET modified unsaturated polyester resin according to claim 1, it is characterised in that: institute in step (1)
The speed for stating stirring is 300r/min.
4. the preparation method of PET modified unsaturated polyester resin according to claim 1, it is characterised in that: institute in step (1)
Insulation reaction is stated to carry out under nitrogen protection.
5. the preparation method of PET modified unsaturated polyester resin according to claim 1, it is characterised in that: institute in step (2)
The boiling point of low boiling point dihydric alcohol is stated lower than 210 DEG C.
6. the preparation method of PET modified unsaturated polyester resin according to claim 1, it is characterised in that: each reactant
Dosage is as follows:
The weight ratio of the useless PET and the dihydric alcohol is 1:0.7-1:1.2；
The weight ratio of the useless PET and the glycerol is 1:0.3-1:0.8；
The weight ratio of the useless PET and the unsaturated dicarboxylic acid anhydride is 1:0.8-1:1.4；
The molar ratio of the monohydric alcohol and the glycerol is 1:0.9-1:1.2；
The molar ratio of total carboxylic acid and total polyalcohol is 1:0.9-1:1.05；
The additional amount of the catalyst is that the useless PET weight is 0.3%；
The additional amount of the styrene is unsaturated polyester resin total weight 35%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811347259.8A CN109553761A (en) | 2018-11-13 | 2018-11-13 | A kind of preparation method of PET modified unsaturated polyester resin |
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| CN201811347259.8A CN109553761A (en) | 2018-11-13 | 2018-11-13 | A kind of preparation method of PET modified unsaturated polyester resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112408869A (en) * | 2020-11-19 | 2021-02-26 | 贺州学院 | Styrene-free artificial stone and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775586A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Novel polyester-polyether polyatomic alcohol and preparation method thereof |
| KR20140122499A (en) * | 2013-04-10 | 2014-10-20 | 건설화학공업주식회사 | Unsaturated polyester resin for Polymer Concrete using PET by-product, and the manufacturing method |
| CN105367769A (en) * | 2015-12-17 | 2016-03-02 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing PET |
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2018
- 2018-11-13 CN CN201811347259.8A patent/CN109553761A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775586A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Novel polyester-polyether polyatomic alcohol and preparation method thereof |
| KR20140122499A (en) * | 2013-04-10 | 2014-10-20 | 건설화학공업주식회사 | Unsaturated polyester resin for Polymer Concrete using PET by-product, and the manufacturing method |
| CN105367769A (en) * | 2015-12-17 | 2016-03-02 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing PET |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112408869A (en) * | 2020-11-19 | 2021-02-26 | 贺州学院 | Styrene-free artificial stone and preparation method thereof |
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