CN106349502B - Mixed type polyacid ester plasticizer and preparation method thereof - Google Patents
Mixed type polyacid ester plasticizer and preparation method thereof Download PDFInfo
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- CN106349502B CN106349502B CN201610735842.0A CN201610735842A CN106349502B CN 106349502 B CN106349502 B CN 106349502B CN 201610735842 A CN201610735842 A CN 201610735842A CN 106349502 B CN106349502 B CN 106349502B
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- 150000002148 esters Chemical class 0.000 title claims abstract description 44
- 239000004014 plasticizer Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229920000728 polyester Polymers 0.000 claims abstract description 33
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- XLJSMWDFUFADIA-UHFFFAOYSA-N 1,3-diethylimidazol-1-ium Chemical compound CCN1C=C[N+](CC)=C1 XLJSMWDFUFADIA-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 235000011837 pasties Nutrition 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000010792 warming Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229960002050 hydrofluoric acid Drugs 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920004933 Terylene® Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 2
- 230000034659 glycolysis Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 102000054766 genetic haplotypes Human genes 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 n-octyl alcohol Ester Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
- C07C69/82—Terephthalic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a kind of methods of the byproduct comprehensive utilization generated in inclined acid anhydride subtractive process.The following steps are included: being that catalyst regulates and controls the molecular mass and distribution for the diol-lipid compound that alcoholysis obtains by the selection of catalyst content and technological temperature with 1,3- diethyl imidazolium boron fluorate using polyester waste material as raw material.When molecular mass and distribution is in OK range, the purification residue and isooctanol of inclined acid anhydride is added, carries out esterification/ester exchange reaction, obtains the preferable mixed type polyacid ester plasticizer of the performance indicators such as acidity, heating loss and flash-point.Compared with prior art, more preferable in the multinomial performances index such as acidity, heating loss and flash-point, with excellent heat resistance and processing convenience, it can satisfy the requirement of general field plasticizer；Preparation method is simple, easily operated, equipment cost is low and pollution-free simultaneously；It can produce huge Social benefit and economic benefit, popularity be suitble to use.
Description
Technical field
The invention belongs to the applications of inclined acid anhydride purification residue and Reclaim of PET Scrap to utilize field；It is related to by the essence of inclined acid anhydride
The mixed type polyacid ester plasticizer and preparation method thereof that residue processed is synthesized with waste and old polyester material alcoholysis material.
Background technique
Polyester is mainly for the production of fiber, polyester bottles and film etc..The source of polyester waste material is mainly to produce in production process
Raw dead meal, leftover pieces, waste polyester bottle and polyester film etc..With the fast development of polyester industrial, polyester waste material is increasingly
Increase, it is domestic to have reached hundreds of thousands ton every year.It is its light weight, bulky although these polyesters waste materials toxicity itself is little,
It is difficult to degrade under field conditions (factors), can not only makes a big impact to environment, and causes the huge wasting of resources.As change give up into
Important channel that is precious and solving ecological environmental pollution, develops the recovery and utilization technology of polyester waste material increasingly by countries in the world
Attention.
The recovery and utilization technology of existing polyester waste material specifically includes that Methanolysis, glycolysis alcoholysis and hydrolysis.Although above-mentioned
Method can by depolymerizing polyester scrap be monomer or industrial chemicals, realize polyester waste material recycle, but the above method there are still
Many unfavorable factors, such as: the organic solvent used in degradation process is volatile, pollutes environment；Severe reaction conditions, it usually needs
High temperature and pressure；Glycolysis alcoholysis product is more complex, wherein there is many oligomers；Acid-base solution in hydrolytic process, which can corrode, to be set
Standby, pollution environment.
On the other hand, O-phthalic acid type monomer ester plasticizer is the most commonly used a kind of plastic additive in China, is weight
One of fine chemical product wanted has the mechanical property for improving the products such as plastics, rubber and high molecular material particularly significant
Effect, occupy ninety percent or so in domestic external plasticizer industrial products, mainly include dibutyl phthalate and O-phthalic
Dioctyl phthalate etc..However, people have found in use, there are lasting bio-toxicity and environment for phthalic ester plasticizer
Harm.Many countries have taken corresponding restriction, for example, U.S. FDA and European Union's Reach regulation have forbidden this kind of increasing
It moulds agent and is used for food packaging, cosmetics and toy for children.In order to overcome drawbacks described above, people are dedicated to research and use other types
Haplotype ester plasticizer replace phthalic ester plasticizer, wherein studying more plasticizer is terephthalate
Class plasticizer.In order to sufficiently reduce cost, has existed produce terephthalate using Waste Polyester edman degradation Edman in the prior art
The process route of class plasticizer.For example, Chinese patent application CN1034534A discloses the terylene leftover bits and pieces using terylene textile mills
Material production dioctyl terephthalate method, also needed after ester exchange reaction by distillation, in and repeatedly washing and filtering etc.
Many processes.However, above-mentioned process route products obtained therefrom is in the performance indicators such as acidity, heating loss and flash-point lower than common
Dioctyl terephthalate causes it bad in terms of heat resistance and processing convenience；It is not competed in terms of production cost simultaneously
Advantage.
For disadvantages mentioned above, people begin one's study different pungent for producing terephthalic acid (TPA) two using isooctanol substitution n-octyl alcohol
Ester.But it equally exists that there is also disadvantages mentioned above when obtaining the product using Waste Polyester edman degradation Edman, is not able to satisfy application request.
Inventors have found that the recovery and utilization technology based on polyester waste material, by the regulation of process conditions, obtain molecular weight compared with
Then low and narrow distribution diol-lipid compound is added inclined acid anhydride purification residue, then esterification occurs with isooctanol,
Mixed type polyacid ester plasticizer is obtained, mixed type polyacid ester plasticizer is available meets higher practical application for this
It is required that.
Summary of the invention
The object of the invention first is that overcoming the deficiencies of the prior art and provide the performances such as a kind of acidity, heating loss and flash-point
The preferable mixed type polyacid ester plasticizer of index.
The second object of the present invention is to providing a kind of method for preparing above-mentioned mixed type polyacid ester plasticizer.Method letter
It is single, easily operated, equipment cost is low and pollution-free.
A kind of preparation method of mixed type polyacid ester plasticizer, this method include the following steps:
1) polyester waste material, neopentyl glycol and catalyst of crushing are added in the reaction vessel, three's weight ratio is 1:(3-
5): (0.05-0.15)；
2) it is stirred to react mixture and it is made slowly to heat up, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 190 DEG C, the temperature of reaction mixture is controlled between 190-210 DEG C, reaction time 3-
12h；
4) it is cooled to 140-150 DEG C, isolates undegradable polyester waste material；Residue is cooled to room temperature and dries, and obtains
Light yellow pasty masses；
5) by above-mentioned light yellow pasty masses, inclined acid anhydride purification residue and isooctanol according to weight ratio (2.0-3.0): 1:
(6.0-8.0) is added in reaction vessel, 160-180 DEG C is warming up under stirring, vacuum dehydration 2-4h；It is then added and accounts for inclined acid anhydride
The tetrabutyl titanate catalyst of quality 1% is warming up to 220-240 DEG C of progress esterification/ester exchange reaction, when acidity≤0.05%
When, esterification terminates, and obtains reaction solution；
6) reaction solution is cooled to 100 DEG C hereinafter, appropriate activated carbon is added, then heats to 200-220 DEG C, vacuum distillation
The ethylene glycol and excessive isooctanol generated in ester exchange reaction is removed, after distillation, is filtered while hot, cooling obtains mixed type
Polyacid ester plasticizer.
In step 1), catalyst is selected from 1,3- diethyl imidazolium boron fluorate.Preferably, the polyester waste material of crushing, new
The weight ratio of pentanediol and catalyst is 1:(3.2-4.5): (0.07-0.13)；It is highly preferred that the polyester waste material crushed, new penta
The weight ratio of two pure and mild catalyst is 1:(3.4-4.2): (0.09-0.11)；Most preferably, the polyester waste material of crushing, new penta 2
The weight ratio of pure and mild catalyst is 1:(3.6-4.0): 0.10.
In step 2), heating rate be preferably must be held between 10-20 DEG C/h.If heating rate is higher than 20 DEG C/h,
Alcoholysis product is more complex, including a variety of oligomers and small molecule dihydric alcohol.If heating rate is lower than 10 DEG C/h, alcoholysis reaction
Rate is not high, while alcoholysis product molecular weight distribution is wider.Preferably, heating rate is 12-18 DEG C/h；It is highly preferred that heating speed
Rate is 14-16 DEG C/h；Most preferably, heating rate is 15 DEG C/h.
In step 3), the boiling point of neopentyl glycol is 210 DEG C or so.When the temperature of control reaction mixture is in 190-210
When between DEG C, the polyester waste material and neopentyl glycol of crushing are uniformly mixed, fully reacting.In reaction process, prepare respectively different dense
The ethylene glycol and neopentyl glycol mixed liquor of degree detect the alcoholysis progress of polyester waste material by liquid-phase chromatography method.The result shows that instead
After answering 1h, alcoholysis reaction rate has reached 65%, and as reaction constantly carries out, alcoholysis reaction rate is constantly increased, and reaches 3h
When above, alcoholysis reaction rate reaches 94% or more, and alcoholysis reaction rate increases slow with the reaction time thereafter.It is therefore preferred that anti-
It is 4-10h between seasonable；It is highly preferred that the reaction time is 5-8h；Most preferably, reaction time 6h.
In step 4), residue is cooled to room temperature and dries, and obtains light yellow pasty masses.Wherein, the drying side
Formula is vacuum drying.The average molecular mass Mn of the light yellow pasty masses is between 521-643；Hydroxyl value test result is 195-
210mgKOH/g.By the way that LC-MS analysis, the above are following compounds A for the light yellow pasty masses 86%.By
This may determine that the light yellow pasty masses are mainly the mixture by the compound A diol-lipid compound formed.
In step 5), by above-mentioned light yellow pasty masses, inclined acid anhydride purification residue and isooctanol according to weight ratio (2.0-
3.0) it: 1:(6.0-8.0) is added in reaction vessel.Wherein, as previously mentioned, the average molecular weight of above-mentioned light yellow pasty masses is
521-643, and the terephthalic acid (TPA) of about equivalent 2 molar equivalents of the above-mentioned light yellow pasty masses of 1 molar equivalent, with inclined acid anhydride essence
Residue processed collectively constitutes mixed type polyacid.Only above-mentioned light yellow pasty masses will also could be with by ester exchange reaction
Isooctanol is reacted, and directly with isooctanol esterification occurs for acid anhydride purification residue partially.Preferably, above-mentioned light yellow paste
The weight ratio of substance, inclined acid anhydride purification residue and isooctanol is (2.5-3.0): 1:(7.0-8.0)；It is highly preferred that weight ratio is
(2.8-3.0): 1:(7.5-8.0)；Most preferably, weight ratio 3.0:1:8.0.
In step (6), reaction solution is cooled to 100 DEG C or less, in order to be added under safety condition appropriate living
Property carbon, otherwise it is possible that bumping phenomenon, there are security risks.The additional amount of activated carbon is generally the 0.1- of reaction solution weight
0.5%.Preferably, the additional amount of activated carbon is the 0.1-0.3% of reaction solution weight；It is highly preferred that the additional amount of activated carbon is
The 0.1-0.2% of reaction solution weight；Most preferably, the additional amount of activated carbon is the 0.15% of reaction solution weight.
In step (6), vacuum distillation removes the ethylene glycol and excessive isooctanol generated in ester exchange reaction, has distilled
Complete mark is that there is no condensed fluid appearance in the container observed in visor for receiving ethylene glycol and isooctanol.
On the other hand, the present invention provides a kind of mixed type polyacid ester plasticizers obtained by above-mentioned preparation method.
Inventors have found that, with 1,3- diethyl imidazolium boron fluorate for catalyst, passing through catalysis using polyester waste material as raw material
The selection of agent content and technological temperature regulates and controls the molecular mass and distribution for the diol-lipid compound that alcoholysis obtains.
When molecular mass and distribution is in OK range, inclined acid anhydride purification residue and isooctanol is added, be esterified/transesterification is anti-
It answers, obtains the preferable mixed type polyacid ester plasticizer of the performance indicators such as acidity, heating loss and flash-point.
Compared with prior art, the present invention has following advantage:
1) mixed type polyacid ester plasticizer of the invention is in the multinomial performances index such as acidity, heating loss and flash-point
More preferably, with excellent heat resistance and processing convenience, it can satisfy the requirement of general field plasticizer.
2) mixed type polyacid ester plasticizer preparation method of the invention is simple, easily operated, equipment cost is low and nothing
Pollution；It can produce huge Social benefit and economic benefit, popularity be suitble to use.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the contents of the present invention, those skilled in the art
The present invention can be made various changes or modifications, such equivalent forms are equally fallen within defined by the application the appended claims
Range.
Embodiment 1:
Mixed type polyacid ester plasticizer of the invention is prepared first, in accordance with following method, this method includes following step
It is rapid:
1) polyester waste material, neopentyl glycol and catalyst 1,3- diethyl imidazolium boron fluoric acid of crushing are added in the reaction vessel
Salt, three's weight are respectively 20g, 68g and 1.8g；
2) it is stirred to react mixture and it is made slowly to heat up, heating rate is 14 DEG C/h；
3) after temperature is higher than 190 DEG C, the temperature of reaction mixture is controlled between 190-210 DEG C, reaction time 5h；
4) it is cooled to 140-150 DEG C, isolates undegradable polyester waste material；Residue is cooled to room temperature and dries, and obtains
Light yellow pasty masses；The average molecular mass Mn of the light yellow pasty masses is 574；Hydroxyl value test result is 196mgKOH/
g；The light yellow pasty masses 92% are compound A.
5) above-mentioned light yellow pasty masses, inclined acid anhydride purification residue and isooctanol are added according to weight ratio 3.0:1:8.0
In reaction vessel, 180 DEG C are warming up under stirring, vacuum dehydration 4h；It is then added and accounts for inclined acid anhydride purification residue quality 1%
Tetrabutyl titanate catalyst is warming up to 220 DEG C of progress esterification/ester exchange reactions, when acidity≤0.05%, esterification knot
Beam obtains reaction solution；
6) reaction solution is cooled to 100 DEG C and accounts for the activated carbon of reaction solution weight 0.1% hereinafter, being added, then heat to 220
DEG C, vacuum distillation removes the ethylene glycol and excessive isooctanol generated in ester exchange reaction, after distillation, filters while hot, cold
But mixed type polyacid ester plasticizer is obtained.
Its performance indexes is tested according to the general measuring method of this field.As a result referring to table 1.
Embodiment 2:
Mixed type polyacid ester plasticizer of the invention is prepared first, in accordance with following method, this method includes following step
It is rapid:
1) polyester waste material, neopentyl glycol and catalyst 1,3- diethyl imidazolium boron fluoric acid of crushing are added in the reaction vessel
Salt, three's weight are respectively 20g, 75g and 2.2g；
2) it is stirred to react mixture and it is made slowly to heat up, heating rate is 15 DEG C/h；
3) after temperature is higher than 190 DEG C, the temperature of reaction mixture is controlled between 190-210 DEG C, reaction time 6h；
4) it is cooled to 140-150 DEG C, isolates undegradable polyester waste material；Residue is cooled to room temperature and dries, and obtains
Light yellow pasty masses；The average molecular mass Mn of the light yellow pasty masses is 521；Hydroxyl value test result is 209mgKOH/
g；The light yellow pasty masses 86% are compound A.
5) above-mentioned light yellow pasty masses, inclined acid anhydride purification residue and isooctanol are added according to weight ratio 2.5:1:7.0
In reaction vessel, 160 DEG C are warming up under stirring, vacuum dehydration 2h；It is then added and accounts for inclined acid anhydride purification residue quality 1%
Tetrabutyl titanate catalyst is warming up to 240 DEG C of progress esterification/ester exchange reactions, when acidity≤0.05%, esterification knot
Beam obtains reaction solution；
6) reaction solution is cooled to 100 DEG C and accounts for the activated carbon of reaction solution weight 0.2% hereinafter, being added, then heat to 200
DEG C, vacuum distillation removes the ethylene glycol and excessive isooctanol generated in ester exchange reaction, after distillation, filters while hot, cold
But mixed type polyacid ester plasticizer is obtained.
Its properties is measured in the same manner as shown in Example 1.As a result it is recorded in table 1.
Embodiment 3:
Mixed type polyacid ester plasticizer of the invention is prepared first, in accordance with following method, this method includes following step
It is rapid:
1) polyester waste material, neopentyl glycol and catalyst 1,3- diethyl imidazolium boron fluoric acid of crushing are added in the reaction vessel
Salt, three's weight are respectively 20g, 84g and 2g；
2) it is stirred to react mixture and it is made slowly to heat up, heating rate is 16 DEG C/h；
3) after temperature is higher than 190 DEG C, the temperature of reaction mixture is controlled between 190-210 DEG C, reaction time 8h；
4) it is cooled to 140-150 DEG C, isolates undegradable polyester waste material；Residue is cooled to room temperature and dries, and obtains
Light yellow pasty masses；The average molecular mass Mn of the light yellow pasty masses is 643；Hydroxyl value test result is 201mgKOH/
g；The light yellow pasty masses 88% are compound A.
5) above-mentioned light yellow pasty masses, inclined acid anhydride purification residue and isooctanol are added according to weight ratio 2.8:1:7.5
In reaction vessel, 170 DEG C are warming up under stirring, vacuum dehydration 3h；It is then added and accounts for inclined acid anhydride purification residue quality 1%
Tetrabutyl titanate catalyst is warming up to 230 DEG C of progress esterification/ester exchange reactions, when acidity≤0.05%, esterification knot
Beam obtains reaction solution；
6) reaction solution is cooled to 100 DEG C and accounts for the activated carbon of reaction solution weight 0.15% hereinafter, being added, then heated to
210 DEG C, vacuum distillation removes the ethylene glycol and excessive isooctanol generated in ester exchange reaction, after distillation, filters while hot,
Cooling obtains mixed type polyacid ester plasticizer.
Its properties is measured in the same manner as shown in Example 1.As a result it is recorded in table 1.
Comparative example 1:
Mixed type polyacid ester plasticizer, the pale yellow color of step 5) are prepared according to the identical preparation method of embodiment 1
Shape substance weight keeps same as Example 1, but step 5) saves slightly biased acid anhydride and refines residue, becomes the following steps: will be above-mentioned shallow
Yellow pasty masses and isooctanol are added in reaction vessel according to weight ratio 3.0:8.0,180 DEG C are warming up under stirring, very
Sky dehydration 4h；The tetrabutyl titanate catalyst for accounting for light yellow pasty masses quality 0.33% is then added, is warming up to 220 DEG C of progress
Esterification/ester exchange reaction, when acidity≤0.05%, esterification terminates, and obtains reaction solution.Finally obtain the more of comparative example 1
First acid ester type plasticizer.Its properties is measured in the same manner as shown in Example 1.As a result it is recorded in table 1.
Its tensile strength and compressive strength and shear strength at room temperature is measured in the same manner as shown in Example 1.
As a result it is recorded in table 1.
The performance indicator of plasticizer product obtained by the different embodiments of table 1
From the point of view of the acidity of table 1, the plasticizer product acidity that the embodiment of the present application 1-3 is obtained is up to 0.014%.And compare
The plasticizer product obtained compared with example 1 is higher than 0.020, according to concerned countries criterion, belongs to substandard product.In addition, this Shen
Please obtained heating loss maximum value≤0.12% of plasticizer product of embodiment 1-3, and the plasticizer product that comparative example 1 obtains
Then≤0.22%.Obviously, the acidity and heating loss performance of present invention gained plasticizer product are substantially better than comparative example.
On the other hand, the flash-point value for the plasticizer product that 1-3 of the embodiment of the present invention is obtained and 200 DEG C of heat-stable times are same
It is substantially better than the plasticizer product that comparative example 1 obtains, this shows the plasticizer product of the embodiment of the present invention 1 in heat resistance and processing
Comparative example is substantially better than in terms of convenience.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., is all included in the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of mixed type polyacid ester plasticizer, this method include the following steps:
1) polyester waste material, neopentyl glycol and catalyst of crushing are added in the reaction vessel, three's weight ratio is 1:(3-5):
(0.05-0.15)；
2) it is stirred to react mixture and it is made slowly to heat up, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 190 DEG C, the temperature of reaction mixture is controlled between 190-210 DEG C, reaction time 3-12h；
4) it is cooled to 140-150 DEG C, isolates undegradable polyester waste material；Residue is cooled to room temperature and dries, and obtains pale yellow
Color pasty masses, the light yellow pasty masses 86% compound A following the above are chemical formula,
；
5) by above-mentioned light yellow pasty masses, the purification residue of inclined acid anhydride and isooctanol according to weight ratio (2.0-3.0): 1:
(6.0-8.0) is added in reaction vessel, 160-180 DEG C is warming up under stirring, vacuum dehydration 2-4h；It is then added and accounts for inclined acid anhydride
Purification residue quality 1% tetrabutyl titanate catalyst, be warming up to 220-240 DEG C of progress esterification/ester exchange reaction, work as acid
When degree≤0.05%, esterification terminates, and obtains reaction solution；
6) reaction solution is cooled to 100 DEG C hereinafter, appropriate activated carbon is added, then heats to 200-220 DEG C, vacuum distillation removes
The ethylene glycol and excessive isooctanol generated in ester exchange reaction, after distillation, is filtered while hot, and it is polynary that cooling obtains mixed type
Acid ester type plasticizer.
2. preparation method according to claim 1, wherein the catalyst of the step 1) is selected from 1,3- diethyl imidazolium boron
Fluorate.
3. preparation method according to claim 1 or 2, wherein in the step 1), the polyester waste material of crushing, new penta 2
The weight ratio of pure and mild catalyst is 1:(3.4-4.2): (0.09-0.11).
4. preparation method according to claim 1 or 2, wherein in the step 2), heating rate is 14-16 DEG C/h.
5. preparation method according to claim 1 or 2, wherein in the step 3), reaction time 5-8h.
6. preparation method according to claim 1 or 2, wherein in the step 4), the light yellow pasty masses are put down
Average molecular weight Mn is between 521-643；Hydroxyl value test result is 195-210mgKOH/g.
7. preparation method according to claim 1 or 2, wherein in the step 5), the light yellow pasty masses, partially
The purification residue of acid anhydride and the weight ratio of isooctanol are (2.5-3.0): 1:(7.0-8.0).
8. preparation method according to claim 1 or 2, wherein in the step 6), the additional amount of the activated carbon is anti-
Answer the 0.1-0.5% of liquid weight.
9. a kind of mixed type polyacid ester plasticizer, which is characterized in that use the described in any item method systems of claim 1-8
It is standby.
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| CN102030652A (en) * | 2010-11-23 | 2011-04-27 | 无锡双象化学工业有限公司 | Industrialized production method for synthesizing trioctyl trimellitate through composite catalysis |
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