CN106349502A - Mixed type polybasicester plasticizer and preparation method thereof - Google Patents
Mixed type polybasicester plasticizer and preparation method thereof Download PDFInfo
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- CN106349502A CN106349502A CN201610735842.0A CN201610735842A CN106349502A CN 106349502 A CN106349502 A CN 106349502A CN 201610735842 A CN201610735842 A CN 201610735842A CN 106349502 A CN106349502 A CN 106349502A
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 230000032050 esterification Effects 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 235000011837 pasties Nutrition 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 239000000376 reactant Substances 0.000 claims description 25
- 150000008065 acid anhydrides Chemical class 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 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
- 238000012360 testing method Methods 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- XLJSMWDFUFADIA-UHFFFAOYSA-N 1,3-diethylimidazol-1-ium Chemical compound CCN1C=C[N+](CC)=C1 XLJSMWDFUFADIA-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 abstract 3
- MHPYNOGXZXFDBL-UHFFFAOYSA-N [B].C(C)N1CN(C=C1)CC Chemical compound [B].C(C)N1CN(C=C1)CC MHPYNOGXZXFDBL-UHFFFAOYSA-N 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 230000015556 catabolic process 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
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 2
- 230000034659 glycolysis Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 229920002799 BoPET Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 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
- 150000007519 polyprotic acids Chemical class 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
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis 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
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying 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 method for comprehensively utilizing by-products generated in a trimellitic anhydride refining process. The method comprises the following steps: taking polyester waste as a raw material, taking 1,3-diethyl imidazole boron fluoborate as a catalyst, selecting the content and the process temperature of the catalyst, and regulating and controlling molecular size and distribution of a polyethylene terephthalate compound which is obtained by alcoholysis; and when the molecular size and the distribution are in a suitable range, adding refined residues of trimellitic anhydride and carrying out esterification/ester interchange reaction on the refined residues of the trimellitic anhydride and isooctanol to obtain a mixed type polybasicester plasticizer of which performance indexes such as acidity, heating loss and flashing point are good. Compared with the prior art, the mixed type polybasicester plasticizer has better performance indexes such as the acidity, the heating loss and the flashing point, has excellent heat resistance and processing convenience, and can meet requirements of plasticizers in the conventional field. Meanwhile, the preparation method is simple, easy to operate, low in cost of equipment and pollution-free; social benefit and economic benefit are huge; and the method is suitable for being generally popularized and used.
Description
Technical field
The invention belongs to inclined acid anhydride refines the application of residue and Reclaim of PET Scrap utilizes field；It is related to by the essence of inclined acid anhydride
Mixed type polyprotic acid ester plasticizer that residue processed is obtained with the synthesis of waste and old polyester material alcoholysis material and preparation method thereof.
Background technology
Polyester is mainly for the production of fiber, polyester bottles and thin film etc..The source of polyester waste material is mainly in production process produces
The dead meal of life, leftover pieces, waste polyester bottle and mylar etc..With the fast development of polyester industrial, polyester waste material is increasingly
Increase, domestic reached hundreds of thousands ton every year.It is although these polyesters waste materials toxicity itself is less, its light weight, bulky,
It is difficult to degrade under field conditions (factors), not only environment can be made a big impact, and cause the huge wasting of resources.As change give up into
Important channel that is precious and solving ecological environmental pollution, the recovery and utilization technology of exploitation polyester waste material is increasingly subject to countries in the world
Attention.
The recovery and utilization technology of existing polyester waste material specifically includes that Methanolysis, glycolysis alcoholysis and hydrolysis.Although it is above-mentioned
Depolymerizing polyester scrap can be monomer or industrial chemicals by method, realize polyester waste material and recycle, but said method still suffers from
Many unfavorable factors, such as: the organic solvent used in degradation process is volatile, pollute environment；Severe reaction conditions, it usually needs
High Temperature High Pressure；Glycolysis alcoholysis product is more complicated, wherein has many oligomers；Acid-base solution in hydrolytic process can corrode and sets
Standby, pollution environment.
On the other hand, O-phthalic acid type monomer ester plasticizer is that China uses most class plastic additives, is weight
One of fine chemical product wanted, has particularly significant to the mechanical property improving the products such as plastics, rubber and macromolecular material
Effect, occupy ninety percent about in domestic external plasticizer industrial products, main include dibutyl phthalate and O-phthalic
Dioctyl phthalate etc..However, people find in use, there is lasting bio-toxicity and environment in phthalic ester plasticizer
Harm.Much country has taken corresponding restriction, and for example, U.S. fda and European Union's reach regulation have all forbidden this kind of increasing
Mould agent for packaging for foodstuff, cosmetics and toy for children.In order to overcome drawbacks described above, people are devoted to research using other types
Haplotype ester plasticizer replace phthalic ester plasticizer, wherein studying more plasticizer is terephthalate
Class plasticizer.For abundant reduces cost, exist in prior art and produced terephthalate using Waste Polyester edman degradation Edman
The process route of class plasticizer.For example, Chinese patent application cn1034534a is disclosed and is got a foothold using the terylene of terylene textile mills
The method that material produces DOTP, also needs through distillation after ester exchange reaction, neutralizes, repeatedly washes and filter etc.
Many flow processs.However, above-mentioned process route products obtained therefrom is less than in the performance indications such as acidity, heating loss and flash-point commonly using
DOTP, lead to its thermostability and processing convenience in terms of not good；Production cost aspect is not competing simultaneously
Strive advantage.
For disadvantages mentioned above, people begin one's study using isooctanol substitute n-octyl alcohol be used for producing p-phthalic acid two different pungent
Ester.But obtain equally existing during this product using Waste Polyester edman degradation Edman and also there is disadvantages mentioned above it is impossible to meet application request.
Inventor finds, based on the recovery and utilization technology of polyester waste material, by the regulation and control of process conditions, obtains molecular weight relatively
The diol-lipid compound of low and narrow distribution, is subsequently adding inclined acid anhydride and refines residue, then with isooctanol, esterification occurs,
Obtain mixed type polyprotic acid ester plasticizer, this mixed type polyprotic acid ester plasticizer can be met higher practical application
Require.
Content of the invention
One of the object of the invention is to overcome the deficiencies in the prior art, provides the performances such as a kind of acidity, heating loss and flash-point
Index preferably mixed type polyprotic acid ester plasticizer.
The two of the object of the invention are to provide a kind of method preparing above-mentioned mixed type polyprotic acid ester plasticizer.Method letter
Single, easily operated, equipment cost is low and pollution-free.
A kind of preparation method of mixed type polyprotic acid ester plasticizer, the method comprises the following steps:
1) polyester waste material, neopentyl glycol and the catalyst of pulverizing are added in reaction vessel, three's weight is than for 1:(3-5):
(0.05-0.15)；
2) stirring reaction mixture make it slowly heat up, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 190 DEG C, between 190-210 DEG C, the response time is 3-12h to the temperature controlling reactant mixture；
4) it is cooled to 140-150 DEG C, isolate undegradable polyester waste material；Residue is cooled to room temperature and is dried, and obtains pale yellow
Color pasty masses；
5) above-mentioned light yellow pasty masses, inclined acid anhydride are refined residue and isooctanol according to weight ratio (2.0-3.0): 1:(6.0-
8.0) add in reaction vessel, be warming up to 160-180 DEG C under stirring, vacuum dehydration 2-4h；It is subsequently added and account for inclined acid anhydride quality
1% tetrabutyl titanate catalyst, is warming up to 220-240 DEG C and carries out esterification/ester exchange reaction, when acidity≤0.05%, ester
Change reaction to terminate, obtain reactant liquor；
6) reactant liquor is cooled to less than 100 DEG C, adds proper amount of active carbon, then heat to 200-220 DEG C, vacuum distillation removes
The ethylene glycol generating in ester exchange reaction and excessive isooctanol, after distillation finishes, filtered while hot, it is polynary that cooling obtains mixed type
Acid ester type plasticizer.
In step 1) in, catalyst is selected from 1,3- diethyl imidazolium boron fluorate.Preferably, the polyester waste material of pulverizing, new
The weight of pentanediol and catalyst is than for 1:(3.2-4.5): (0.07-0.13)；It is highly preferred that pulverize polyester waste material, new penta
The weight of glycol and catalyst is than for 1:(3.4-4.2): (0.09-0.11)；Most preferably, the polyester waste material of pulverizing, new penta 2
The weight of alcohol and catalyst is than for 1:(3.6-4.0): 0.10.
In step 2) in, heating rate preferably must be held between 10-20 DEG C/h.If heating rate is higher than 20 DEG C/h,
Alcoholysis product is more complicated, including multiple oligomers and small molecule dihydroxylic alcohols.If heating rate is less than 10 DEG C/h, alcoholysis reaction
Rate is not high, and alcoholysis product molecular weight distribution is wider simultaneously.Preferably, heating rate is 12-18 DEG C/h；It is highly preferred that the speed that heats up
Rate is 14-16 DEG C/h；Most preferably, heating rate is 15 DEG C/h.
In step 3) in, the boiling point of neopentyl glycol is 210 DEG C about.When the temperature of control reactant mixture is in 190-210
When between DEG C, the polyester waste material of pulverizing and neopentyl glycol mix homogeneously, reaction is completely.In course of reaction, prepare different dense respectively
The ethylene glycol of degree and neopentyl glycol mixed liquor detect the alcoholysis progress of polyester waste material by liquid-phase chromatography method.Result shows, instead
After answering 1h, alcoholysis reaction rate has reached 65%, and constantly carries out with reaction, and alcoholysis reaction rate constantly raises, and reaches 3h
When above, alcoholysis reaction rate reaches more than 94%, and alcoholysis reaction rate increased slowly with the response time thereafter.It is therefore preferred that it is anti-
It is 4-10h between seasonable；It is highly preferred that the response time is 5-8h；Most preferably, the response time is 6h.
In step 4) in, residue is cooled to room temperature and is dried, and obtains light yellow pasty masses.Wherein, described drying side
Formula is vacuum drying.The mean molecule quantity mn of described light yellow pasty masses is between 521-643；Hydroxyl value test result is 195-
210mgkoh/g.By to LC-MS analysis, described light yellow pasty masses more than 86% are following compounds a.By
This may determine that, the mixture of the diol-lipid compound that described light yellow pasty masses are mainly made up of compound a.
In step 5) in, above-mentioned light yellow pasty masses, inclined acid anhydride are refined residue and isooctanol according to weight ratio (2.0-
3.0): 1:(6.0-8.0) add in reaction vessel.Wherein, as it was previously stated, the mean molecule quantity of above-mentioned light yellow pasty masses is
521-643, and the p-phthalic acid of about equivalent 2 molar equivalents of the above-mentioned light yellow pasty masses of 1 molar equivalent, it is smart with inclined acid anhydride
Residue processed collectively constitutes mixed type polyprotic acid.Only above-mentioned light yellow pasty masses also will could be with through ester exchange reaction
Isooctanol is reacted, and inclined acid anhydride refines residue directly and isooctanol occurs esterification.Preferably, above-mentioned pale yellow color
It is (2.5-3.0): 1:(7.0-8.0 that shape material, inclined acid anhydride refine residue and the weight ratio of isooctanol)；It is highly preferred that weight ratio
For (2.8-3.0): 1:(7.5-8.0)；Most preferably, weight is than for 3.0:1:8.0.
In step (6), reactant liquor is cooled to less than 100 DEG C and lives in right amount in order to add under safety condition
, otherwise it is possible that bumping phenomenon, there is potential safety hazard in property charcoal.The addition of activated carbon is generally the 0.1- of reactant liquor weight
0.5%.Preferably, the addition of activated carbon is the 0.1-0.3% of reactant liquor weight；It is highly preferred that the addition of activated carbon is
The 0.1-0.2% of reactant liquor weight；Most preferably, the addition of activated carbon is the 0.15% of reactant liquor weight.
In step (6), vacuum distillation removes the ethylene glycol generating in ester exchange reaction and excessive isooctanol, has distilled
Complete mark be observe in visor for receive ethylene glycol and isooctanol container in no longer have condensed fluid occur.
On the other hand, the invention provides a kind of mixed type polyprotic acid ester plasticizer being obtained by above-mentioned preparation method.
Inventor finds, with polyester waste material as raw material, with 1,3- diethyl imidazolium boron fluorate for catalyst, by catalysis
Agent content and the selection of technological temperature, the molecular mass and distribution of the diol-lipid compound that alcoholysis is obtained regulates and controls.
When molecular mass and distribution is in OK range, inclined acid anhydride is added to refine residue and isooctanol, carry out being esterified/ester exchange is anti-
Should, obtain the performance indications such as acidity, heating loss and flash-point preferably mixed type polyprotic acid ester plasticizer.
Compared with prior art, the present invention has a following advantage:
1) the mixed type polyprotic acid ester plasticizer of the present invention in the multinomial performance index such as acidity, heating loss and flash-point more
Good, there is excellent thermostability and processing convenience, the requirement of general field plasticizer can be met.
2) the mixed type polyprotic acid ester plasticizer preparation method of the present invention is simple, easily operated, equipment cost is low and pollution-free；
Can have a tremendous social and economic benefits, suitable popularity uses.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read present disclosure, those skilled in the art
The present invention can be made various changes or modifications, these equivalent form of values equally fall within what the application appended claims were limited
Scope.
Embodiment 1:
It is first according to the mixed type polyprotic acid ester plasticizer that following method prepares the present invention, the method includes following step
Rapid:
1) polyester waste material, neopentyl glycol and the catalyst 1 of pulverizing are added in reaction vessel, 3- diethyl imidazolium boron fluorate,
Three's weight is respectively 20g, 68g and 1.8g；
2) stirring reaction mixture make it slowly heat up, heating rate is 14 DEG C/h；
3) after temperature is higher than 190 DEG C, between 190-210 DEG C, the response time is 5h to the temperature controlling reactant mixture；
4) it is cooled to 140-150 DEG C, isolate undegradable polyester waste material；Residue is cooled to room temperature and is dried, and obtains pale yellow
Color pasty masses；The mean molecule quantity mn of described light yellow pasty masses is 574；Hydroxyl value test result is 196mgkoh/g；Institute
Stating light yellow pasty masses 92% is compound a.
5) above-mentioned light yellow pasty masses, inclined acid anhydride are refined residue and isooctanol and add reaction according to weight than 3.0:1:8.0
In container, it is warming up to 180 DEG C under stirring, vacuum dehydration 4h；It is subsequently added and account for the metatitanic acid that inclined acid anhydride refines residue quality 1%
Four butyl ester catalyst, are warming up to 220 DEG C and carry out esterification/ester exchange reaction, when acidity≤0.05%, esterification terminates, and obtains
To reactant liquor；
6) reactant liquor is cooled to less than 100 DEG C, adds the activated carbon accounting for reactant liquor weight 0.1%, then heat to 220 DEG C,
Vacuum distillation removes the ethylene glycol generating in ester exchange reaction and excessive isooctanol, after distillation finishes, filtered while hot, and cool down
To mixed type polyprotic acid ester plasticizer.
General measuring method according to this area tests its property indices.Result is referring to table 1.
Embodiment 2:
It is first according to the mixed type polyprotic acid ester plasticizer that following method prepares the present invention, the method includes following step
Rapid:
1) polyester waste material, neopentyl glycol and the catalyst 1 of pulverizing are added in reaction vessel, 3- diethyl imidazolium boron fluorate,
Three's weight is respectively 20g, 75g and 2.2g；
2) stirring reaction mixture make it slowly heat up, heating rate is 15 DEG C/h；
3) after temperature is higher than 190 DEG C, between 190-210 DEG C, the response time is 6h to the temperature controlling reactant mixture；
4) it is cooled to 140-150 DEG C, isolate undegradable polyester waste material；Residue is cooled to room temperature and is dried, and obtains pale yellow
Color pasty masses；The mean molecule quantity mn of described light yellow pasty masses is 521；Hydroxyl value test result is 209mgkoh/g；Institute
Stating light yellow pasty masses 86% is compound a.
5) above-mentioned light yellow pasty masses, inclined acid anhydride are refined residue and isooctanol and add reaction according to weight than 2.5:1:7.0
In container, it is warming up to 160 DEG C under stirring, vacuum dehydration 2h；It is subsequently added and account for the metatitanic acid that inclined acid anhydride refines residue quality 1%
Four butyl ester catalyst, are warming up to 240 DEG C and carry out esterification/ester exchange reaction, when acidity≤0.05%, esterification terminates, and obtains
To reactant liquor；
6) reactant liquor is cooled to less than 100 DEG C, adds the activated carbon accounting for reactant liquor weight 0.2%, then heat to 200 DEG C,
Vacuum distillation removes the ethylene glycol generating in ester exchange reaction and excessive isooctanol, after distillation finishes, filtered while hot, and cool down
To mixed type polyprotic acid ester plasticizer.
Measure its properties according to method same as Example 1.Result record is in Table 1.
Embodiment 3:
It is first according to the mixed type polyprotic acid ester plasticizer that following method prepares the present invention, the method includes following step
Rapid:
1) polyester waste material, neopentyl glycol and the catalyst 1 of pulverizing are added in reaction vessel, 3- diethyl imidazolium boron fluorate,
Three's weight is respectively 20g, 84g and 2g；
2) stirring reaction mixture make it slowly heat up, heating rate is 16 DEG C/h；
3) after temperature is higher than 190 DEG C, between 190-210 DEG C, the response time is 8h to the temperature controlling reactant mixture；
4) it is cooled to 140-150 DEG C, isolate undegradable polyester waste material；Residue is cooled to room temperature and is dried, and obtains pale yellow
Color pasty masses；The mean molecule quantity mn of described light yellow pasty masses is 643；Hydroxyl value test result is 201mgkoh/g；Institute
Stating light yellow pasty masses 88% is compound a.
5) above-mentioned light yellow pasty masses, inclined acid anhydride are refined residue and isooctanol and add reaction according to weight than 2.8:1:7.5
In container, it is warming up to 170 DEG C under stirring, vacuum dehydration 3h；It is subsequently added and account for the metatitanic acid that inclined acid anhydride refines residue quality 1%
Four butyl ester catalyst, are warming up to 230 DEG C and carry out esterification/ester exchange reaction, when acidity≤0.05%, esterification terminates, and obtains
To reactant liquor；
6) reactant liquor is cooled to less than 100 DEG C, adds the activated carbon accounting for reactant liquor weight 0.15%, then heat to 210 DEG C,
Vacuum distillation removes the ethylene glycol generating in ester exchange reaction and excessive isooctanol, after distillation finishes, filtered while hot, and cool down
To mixed type polyprotic acid ester plasticizer.
Measure its properties according to method same as Example 1.Result record is in Table 1.
Comparative example 1:
According to embodiment 1 identical preparation method prepare mixed type polyprotic acid ester plasticizer, step 5) pale yellow color
Shape substance weight keeps same as Example 1, but step 5) save the refined residue of slightly biased acid anhydride, it is changed into the following step: will be above-mentioned shallow
Yellow pasty masses are added in reaction vessel than 3.0:8.0 according to weight with isooctanol, are warming up to 180 DEG C, very under stirring
Empty dehydration 4h；It is subsequently added the tetrabutyl titanate catalyst accounting for light yellow pasty masses quality 0.33%, be warming up to 220 DEG C and carry out
Esterification/ester exchange reaction, when acidity≤0.05%, esterification terminates, and obtains reactant liquor.Finally obtain the many of comparative example 1
First acid ester type plasticizer.Measure its properties according to method same as Example 1.Result record is in Table 1.
Measure tensile strength and compressive strength and the shear strength under its room temperature according to method same as Example 1.
Result record is in Table 1.
The performance indications of the different embodiment gained plasticizer product 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 obtains is up to 0.014%.And compare
The plasticizer product obtaining compared with example 1 is higher than 0.020, according to concerned countries criterion, belongs to substandard product.Additionally, this Shen
Please heating loss maximum≤0.12% of plasticizer product that obtains of embodiment 1-3, and the plasticizer product that comparative example 1 obtains
Then≤0.22%.Obviously, the acidity of gained plasticizer product of the present invention and heating loss performance are substantially better than comparative example.
On the other hand, the flash-point value of the plasticizer product that embodiment of the present invention 1-3 obtains 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 thermostability and processing
Convenience aspect is substantially better than comparative example.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., be all contained within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of mixed type polyprotic acid ester plasticizer, the method comprises the following steps:
1) polyester waste material, neopentyl glycol and the catalyst of pulverizing are added in reaction vessel, three's weight is than for 1:(3-5):
(0.05-0.15)；
2) stirring reaction mixture make it slowly heat up, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 190 DEG C, between 190-210 DEG C, the response time is 3-12h to the temperature controlling reactant mixture；
4) it is cooled to 140-150 DEG C, isolate undegradable polyester waste material；Residue is cooled to room temperature and is dried, and obtains pale yellow
Color pasty masses；
5) by above-mentioned light yellow pasty masses, the refined residue of inclined acid anhydride and isooctanol according to weight ratio (2.0-3.0): 1:
(6.0-8.0) add in reaction vessel, be warming up to 160-180 DEG C under stirring, vacuum dehydration 2-4h；It is subsequently added and account for inclined acid anhydride
Refined residue quality 1% tetrabutyl titanate catalyst, be warming up to 220-240 DEG C and carry out esterification/ester exchange reaction, work as acid
During degree≤0.05%, esterification terminates, and obtains reactant liquor；
6) reactant liquor is cooled to less than 100 DEG C, adds proper amount of active carbon, then heat to 200-220 DEG C, vacuum distillation removes
The ethylene glycol generating in ester exchange reaction and excessive isooctanol, after distillation finishes, filtered while hot, it is polynary that cooling obtains mixed type
Acid ester type plasticizer.
2. preparation method according to claim 1, wherein, described step 1) catalyst be selected from 1,3- diethyl imidazolium boron
Fluorate.
3. preparation method according to claim 1 and 2, wherein, described step 1) in, the polyester waste material of pulverizing, new penta 2
The weight of alcohol and catalyst is than for 1:(3.4-4.2): (0.09-0.11).
4. preparation method according to claim 1 and 2, wherein, described step 2) in, heating rate is 14-16 DEG C/h.
5. preparation method according to claim 1 and 2, wherein, described step 3) in, the response time is 5-8h.
6. preparation method according to claim 1 and 2, wherein, described step 4) in, described light yellow pasty masses flat
Average molecular weight mn is between 521-643；Hydroxyl value test result is 195-210mgkoh/g.
7. preparation method according to claim 1 and 2, wherein, described step 5) in, described light yellow pasty masses, partially
The refined residue of acid anhydride is (2.5-3.0): 1:(7.0-8.0 with the weight ratio of isooctanol).
8. preparation method according to claim 1 and 2, wherein, described step 6) in, the addition of described activated carbon is anti-
Answer the 0.1-0.5% of liquid weight.
9. a kind of mixed type polyprotic acid ester plasticizer is it is characterised in that usage right requires the method system described in any one of 1-8
Standby.
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| CN110372504A (en) * | 2019-08-16 | 2019-10-25 | 南通百川新材料有限公司 | A method of polybasic ester is produced using inclined acid anhydride by-product recycling lighter component |
| CN111533889A (en) * | 2020-03-17 | 2020-08-14 | 北京华腾新材料股份有限公司 | High-thermal-stability migration-resistant polyester plasticizer and preparation method thereof |
| CN114773672A (en) * | 2022-06-05 | 2022-07-22 | 黄山学院 | Low-cost plasticizer for PVC and preparation method thereof |
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| CN110372504A (en) * | 2019-08-16 | 2019-10-25 | 南通百川新材料有限公司 | A method of polybasic ester is produced using inclined acid anhydride by-product recycling lighter component |
| CN110372504B (en) * | 2019-08-16 | 2022-10-04 | 南通百川新材料有限公司 | Method for producing polybasic acid ester by recovering light components from side product of meta-anhydride |
| CN111533889A (en) * | 2020-03-17 | 2020-08-14 | 北京华腾新材料股份有限公司 | High-thermal-stability migration-resistant polyester plasticizer and preparation method thereof |
| CN114773672A (en) * | 2022-06-05 | 2022-07-22 | 黄山学院 | Low-cost plasticizer for PVC and preparation method thereof |
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