CN104130445B - Double citrate plasticizer of a kind of nylon acyl and its production and use - Google Patents
Double citrate plasticizer of a kind of nylon acyl and its production and use Download PDFInfo
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Abstract
The present invention relates to double citrate plasticizer of a kind of nylon acyl and its production and use, prepare for raw material with citric acid, monohydric alcohol, nylon acid.Solving the shortcomings such as existing environment-friendly plasticizer citrate is weak to migrate, and plasticizing efficiency is low, and volatility is high, using raw material is cheap adipic acid by-product nylon acid, effectively reduces production cost.Prepared plasticizer is environment-friendly plasticizer, can be widely used in the fields such as food, medical treatment, toy for children.
Description
Technical field
The present invention relates to a kind of additive or the auxiliary agent of plastics industry, particularly a kind of double citric acid of environment-protecting asepsis nylon acyl
Ester plasticiser and preparation method thereof, is mainly used in package plastics of food and medical apparatus and instruments and toy for children.
Background technology
Plasticizer is one of material additive of yield and consumption figure maximum in the world, and for a long time, plasticizer is mainly with neighbour
Phthalates is main, along with phthalate application in the industry such as food, medical treatment is more and more extensive, and people couple
Its toxicity is the most increasingly paid attention to.U.S. environment protection general bureau, according to the result of study of National Cancer Institute, has limited 6
The application in environmental protection and health etc. require higher industry of kind of phthalate primary plasticizer, as toy, articles for children,
Medical article, packaging material for food etc..Phthalic acid two (2-ethyl) own ester in the plastic of the countries such as outlet European Union
(DEHP or DOP), dibutyl phthalate (DBP), BBP(Butyl Benzyl Phthalate (BBP), diisononyl phthalate
(DINP), the content of diisooctyl phthalate (DIDP) and phthalic acid n-octyl (DNOP) plasticizer does not allows more than
0.1%；Tri-kinds of plasticizers of DEHP, DBP and BBP are prohibited to add toy and all articles for children plastics to；DINP、DIDP
It is, with tri-kinds of plasticizers of DNOP disabling scopes, the toy that possible be put in mouth by three years old and less than three years old child and articles for children are used
Plastics, DOP be only limited in the packaging for foodstuff of high water content use, meat Package must use other nontoxic plasticizer product
Substitute.
Citric acid ester plasticizer safety non-toxic, is one of the first-selected environment-friendlyplasticizer plasticizer of domestic and international plastic industry, at present
Main kind has tributyl citrate (TBC), citroflex A-4 (ATBC), triethyl citrate (TEC).Although
Tributyl citrate (TBC), citroflex A-4 (ATBC), triethyl citrate (TEC) have excellent plasticising effect
Fruit and good tolerance to cold, light resistance, resistance to water, antienzyme, but have compared with traditional phthalic ester plasticizer
Easily precipitation, migrate the problems such as big, volatility is big, thus have impact on the range of citric acid ester plasticizer.For meeting city
The field environmental protection of demand, plasticizer nontoxic, with better function, be badly in need of improving the property of existing citric acid ester plasticizer at present
Can, develop Novel lemon acid ester plasticizer.
In order to improve the resistance to migration of plasticizer and improve the shortcoming that its volatility is high, (carbon number is big to use higher alcohols
In or straight or branched alcohol equal to 8) prepare the citrate of high molecular, be a kind of feasible solution.Such as patent
CN101085736 discloses the technical scheme that a kind of synthesizing citric acid triamyl uses as PVC plasticizer.But, current penta
Alcohol yield is little, and price is high, it is impossible to meets the application demand of high-volume industrial goods plasticizer, and can cause the increasing of use cost
Add.Patent CN101245008 discloses the synthetic method of trioctyl lemon acid.It is extremely low that trioctyl lemon acid can give plasticizer
Volatility and fabulous resistance to migration, but show the right plasticizing efficiency relatively low to plastics.Patent CN102643198 is open
The technical scheme that a kind of synthesizing citric acid three Petiolus Trachycarpi ester uses as PVC plasticizer, in the program, citric acid three Petiolus Trachycarpi ester has
There are the volatility lower than trioctyl lemon acid and more preferable resistance to migration.But it is undesirable to the plasticizing efficiency of some plastics,
In PVC applies, its plasticizing efficiency is only 1.12.
Replacing citric acid hydroxy functional group is also a kind of effective ways improving citric acid ester plasticizer shortcoming,
Patent CN101255114 reports a kind of oleoyl tributyl citrate and preparation method thereof, but containing unsaturation in this plasticizer
C-C key, poor stability, easy oxidation deterioration, apply restricted.Patent CN101255240 reports a kind of octadecanoyl Fructus Citri Limoniae
Acid tributyl and preparation method thereof, uses stearic acid and Phosphorous chloride. reaction, has a large amount of hydrochloric acid, can cause equipment in by-product
Corrosion, production technology is defective, and the plasticizing efficiency of product is undesirable.
Therefore, the most still lacking and a kind of not only had good plasticization effect but also had volatility little, stability is high, anti-migration
Property is good, the safety non-toxic that resistance to extractable is good, prepares the plasticizer product that cheaper starting materials is easy to get.
Summary of the invention
It is an object of the invention to provide the double citrate plasticizer of a kind of nylon acyl, the double citric acid of this novel nylon acyl
Ester type compound is as plastic plasticizer, and volatility is little, and stability is high, and resistance to migration is good, and resistance to extractable is good, low temperature flexibility
Good, safety non-toxic.
The present invention also aims to provide the preparation method of the double citrate plasticizer of a kind of nylon acyl.Preparation technology
Simply, cheaper starting materials is easy to get, and production cost is low, easily realizes large-scale industrial production.
For reaching above goal of the invention, technical scheme is as follows:
The double citrate plasticizer of a kind of nylon acyl, it is a class mixture, and the most each constituent content is by synthesizing this structure
The composition of one of raw material nylon acid determine.Its general structure is as follows:
Wherein n=2-4, R are the alkyl of C2-C13.
A kind of preparation method of the double citrate plasticizer of nylon acyl, with citric acid, monohydric alcohol, nylon acid as raw material, logical
Cross to comprise the steps of and prepare: step 1: the preparation of citrate A: citric acid and excess monohydric alcohol are urged at acidic catalyst
Change lower reaction, obtain citrate A；
R is C2-C13 alkyl.
Step 2: the preparation of nylon anhydride B: nylon acid occurs dehydration to obtain under modified molecular sieve catalyst is catalyzed
Nylon anhydride B；
Step 3: the preparation of the double citrate of nylon acyl: nylon anhydride B and citrate A mixing, at catalyst and auxiliary agent
Carry out acylation reaction under effect and obtain the double citrate product of nylon acyl.
R is C2-C13 alkyl.
In the preparation method of the present invention, step 1 is initiation material with citric acid, C2-C13 saturated monohydroxy alcohol, urges in acidity
Esterification is carried out under agent catalysis, until reaction end, then dealcoholysis, refined, obtain citrate A.Described saturated one
Unit's alcohol can be ethanol, propanol or straight chain and with the butanol of branched structure, amylalcohol, hexanol, enanthol, capryl alcohol, nonyl alcohol, decanol,
One in tridecanol, the one in preferred alcohol, propanol or butanol.The mol ratio of citric acid and saturated monohydroxy alcohol is 1:3-1:
15, preferably 1:4-1:6.
In the preparation method of the present invention, the catalyst of step 1 can be sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, it is also possible to is solid
Body acid such as aluminium sesquioxide, antimony oxide, four titanium oxides, four zirconium oxides etc., preferably aluminium sesquioxide, antimony oxide, four
Titanium oxide, four zirconium oxides.Catalyst amount is the 0.1%-5% of citric acid quality, preferably 1%-2.5%.
In the preparation method of the present invention, the reaction temperature of step 1 is 90 DEG C-160 DEG C.By monitoring acid number judge whether to
Reach reaction end.The stopped reaction when acid number is less than 5mgKOH/g.
In the preparation method of the present invention, step 2 is with nylon acid as raw material, at the HZSM-5 type molecular sieve catalytic that Ti-P is modified
Carry out molecule inner dewatering reaction under agent effect, obtain nylon anhydride B.Gross weight based on HZSM-5 type molecular sieve modified for Ti-P,
Wherein the mass fraction shared by Ti is advisable at 1-4%, and the mass fraction shared by P is that 1-5% is advisable.The HZSM-5 type that Ti-P is modified
Molecular sieve consumption is the 1%-10% of nylon acid quality, preferably 3%-7%, and catalyst can be reused.
In the preparation method of the present invention, described nylon acid is to produce the industrial by-products of adipic acid, for mixing C4-C6 bis-
Unit's acid, comprises adipic acid, succinic acid, 1,3-propanedicarboxylic acid.The most each component percentage is about: succinic acid 15%-35%, penta 2
Acid 40%-60%, adipic acid 15%-35%, based on component gross weight.
In the preparation method of the present invention, HZSM-5 type molecular sieve catalyst preparation method modified for Ti-P is as follows:
Weigh a certain amount of H3PO4It is dissolved in a certain amount of deionized water, is configured to the phosphoric acid water of 10wt%-30wt% concentration
Solution, according to phosphate aqueous solution: HZSM-5 type molecular sieve=1:2-1:5 (mass ratio) mix homogeneously:, stir at 45 DEG C-60 DEG C
Mix 4-6 hour, then proceed to baking oven and be dried at 130 DEG C-150 DEG C 3-5 hour, ground once every 1-1.5 hour, cold
Break into pieces the most afterwards, tabletting, screening particle diameter is the granule of 400-600 μm, 600 DEG C-700 DEG C roasting 5-7 hour in Muffle furnace,
To the HZSM-5 type molecular sieve that P is modified.Then heating to 400-500 DEG C, evacuation in hermetic container, persistently passing to pressure is
The TiCl of 1-3 atmospheric pressure4Steam and N2According to the mixed gas of volume ratio 1:40-1:100, keep 4-8 hour, i.e. obtain Ti-
The molecular sieve catalyst that P is modified.
It is a kind of novel pair of modified molecular sieve catalyst that the nylon acid of the present invention prepares nylon anhydride B catalyst, HZSM-
5 type molecular sieves are the high silica alumina ratio molecular sieves that a kind of Industrial Catalysis is conventional, itself have acid site skewness, catalytic life
Short, product is easily in defects such as surface depositions.P modification can effectively change the acid site distribution of molecular sieve surface so that it is distribution
Uniformly, reducing the activity of acid to a certain extent, improve catalytic effect, significantly extend catalyst life, Ti modification can have
Effect changes the internal gutter structure of molecular sieve, increases the space of internal gutter so that reaction molecular easily enters with product molecule
Enter catalytic inner and leave in time so that product will not deposit on a catalyst, improves catalytic efficiency.
In the preparation method of the present invention, the reaction temperature of step 2 is 200 DEG C-380 DEG C, preferably 260 DEG C-320 DEG C.Reaction
Time is 2-4 hour, and reaction terminates rear Filtration of catalyst, and crude product is recrystallization in ether, obtains C4-C6 ring inner-acid anhydride
Mixture i.e. nylon anhydride B.
In the preparation method of the present invention, step 3: the citrate A and the nylon anhydride B that are obtained by step 1 and step 2 are existed
Reacting under catalyst and promoter effect, monitoring reactant acid number stops after reaching reaction end less than stopped reaction during 2mgKOH/g
Only, filtration, deacidification, it is refining to obtain the double citrate product of nylon acyl.
In the preparation method of the present invention, the catalyst of step 3 is the one in p-methyl benzenesulfonic acid, pyridine, triethylamine, consumption
For nylon anhydride B mass 0.5-2%, preferably 1-1.5%.Auxiliary agent is that (Xi'an is blue for commercially available macroporous resin XDA-7 or XDA-8
Dawn, resin processing plant produced), consumption is the 5%-30% of nylon anhydride B mass, preferably 5%-10%.Citrate A and nylon anhydride B
Mol ratio be 10:1-1:1, preferably 4:1-2.5:1.Reaction temperature is 120-155 DEG C, and the response time is 2-4 hour.
The double citrate plasticizer of the nylon acyl prepared by said method has that plasticizing efficiency is high, mobility is low, resistance to takes out
Going out property is good, the advantage that volatility is low.It is applicable to Sensitive Domain such as food, medical packaging, the toy for children etc. of common plastics PVC.
It it is a kind of cheap, environment-friendly plasticizer of excellent performance.And the plasticizer after double being acylated is relative to not being acylated or little point
Son citrate, it is easier to biodegradation, with biodegradable plastic such as polylactic acid (PLA), polyhydroxyalkanoate (PHA,
PHB, PHBV), polycaprolactone (PCL), aliphatic aromatic copolymer, dihydroxylic alcohols dicarboxylic acids aliphatic polyester (PBS), dioxy
Change carbon/epoxy compound composition copolymer (APC), polyvinyl alcohol (PLA), the modified PVA compatibility good, be particularly suitable for and can biological drop
Solve material mixed manufacture environmental protection soft plastic product.
The positive effect of the present invention:
The double citrate plasticizer of the nylon acyl of the present invention, is a asepsis environment-protecting plasticizer, by binary acid by two
The citrate of molecule couples together, and forms macromolecular compound, effectively solves little molecule citrate plasticizer and easily analyse
Go out, the shortcoming such as volatile, easy migration, be a kind of widely applicable plasticizer, prepare raw material sources in citric acid, short chain saturated
Unit's alcohol and nylon acid, citric acid is cheap and easy to get, and nylon acid is to prepare the side-product of adipic acid, and wide material sources are cheap, pass through
Plasticizer low cost prepared by above-mentioned technique, technique is simple, easily realizes industrialized production.
Accompanying drawing explanation
Fig. 1 is the double tributyl citrate GC spectrogram of nylon acyl of embodiment 1 preparation.
Fig. 2 is the double tributyl citrate MS spectrogram of nylon acyl of embodiment 1 preparation
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, it should be noted that embodiment is not intended that this
The restriction of the claimed scope of invention.
Raw materials used it is commercially available product.
Elemental analyser is that Nanjing No.4 Analytical Instrument Co., Ltd. produces, and model is JQ-8
In embodiment, % represents weight %.
GC-MS:Agilent7200Q-TOF
GC analysis condition: analytical conditions for gas chromatography:
Embodiment 1: the preparation of the double tributyl citrate of nylon acyl
A) preparation of tributyl citrate
Adding 1mol citric acid, 4mol n-butyl alcohol, 3g85% phosphoric acid in a kettle., be heated to 110 DEG C, stirring produces back
Stream, after reaction refluxes 2 hours, every sampling in 10 minutes once, measures acid number, the stopped reaction when acid number is less than 5mgKOH/g,
Under nitrogen atmosphere, normal pressure 115-125 DEG C is distilled off unreacted raw material and by-product, obtains tributyl citrate 330g, yield
About 91.6%.
B) preparation of nylon anhydride
Prepared by catalyst:
Weigh the H of 7.5g85%3PO4It is dissolved in 30g deionized water, then mixs homogeneously with the HZSM-5 type molecular sieve of 98g,
Stir 5 hours at 60 DEG C, then proceed to 150 DEG C of oven dryings 4 hours, ground once every 1 hour, break into pieces after cooling,
Tabletting, screens 400-600 μm granule, 600 DEG C of roastings 5 hours in Muffle furnace, obtains the modified HZSM-5 type molecular sieve of P,
Then heat to 450 DEG C, evacuation in hermetic container, persistently pass to the TiCl that pressure is 1 atmospheric pressure4Steam and N2According to
The mixed gas of volume ratio 1:40, keeps 4 hours, i.e. obtains P-Ti modified HZSM-5 type molecular sieve catalyst, passes through elementary analysis
P content about 2.7% in instrument detection catalyst, Ti content 1.32%.
Add nylon acid 120g, P-Ti modified HZSM-5 type molecular sieve 10g in a kettle., be passed through nitrogen, be heated to 260
DEG C, start stirring, and persistently overheating until 300 DEG C, stopping heating, cooling after reacting 3 hours, filter, catalyst can weigh
Multiple use, obtains own inner-acid anhydride, fourth inner-acid anhydride, the mixture of penta inner-acid anhydride, i.e. nylon anhydride, product about 90g.
C) preparation of the double tributyl citrate of nylon acyl
Addition tributyl citrate 330g in a kettle., nylon anhydride 35g, consisting of succinic acid 25.5%, penta 2
Acid 41.3%, adipic acid 33.2%, (purchased from Yancheng Lang De Chemical Company outside nylon acid, for GB top grade product, do not contain
Water, other impurity contents are less than 1%, ignore) triethylamine 0.5g, XDA-7 macroporous resin 5g.It is passed through nitrogen, is warming up to 135
DEG C, start stirring, every 10 minutes sampling detecting acid numbers after reacting 3 hours, the stopped reaction when acid number is less than 2mgKOH/g, mistake
Filter, the Na of addition 100g2%2CO3Washed once, then with again with 150g deionized water wash once, reduce pressure distillation dehydration,
To double tributyl citrate 220g of nylon acyl, yield about 95%.
Being analyzed products therefrom with GC-MS, as shown in Figure 1, 2, analysis result is spectrogram:
Embodiment 2: the preparation of the double triethyl citrate of nylon acyl
A) preparation of triethyl citrate
Adding 1mol citric acid, 3.5mol ethanol, 2g85% phosphoric acid in a kettle., be heated to 95 DEG C, stirring produces back
Stream.After should refluxing 1.5 hours, every sampling in 10 minutes once, measuring acid number, when acid number is less than 5mgKOH/g, stopped reaction is only
Reaction, air-distillation under nitrogen atmosphere, steam unreacted alcohol at 90-110 DEG C, obtain triethyl citrate 255g, yield is about
92.3%.
B) preparation of nylon anhydride is as described in step b in embodiment 1.Nylon acid composition is identical.
C) preparation of the double triethyl citrate of nylon acyl
Add triethyl citrate 255g and nylon anhydride 23g, pyridine 0.12g, XDA-8 macroporous resin in a kettle.
2g, is passed through nitrogen, is warming up to 120 DEG C, starts stirring, every 10 minutes sampling detecting acid numbers after reacting 3 hours, when being less than
Stopped reaction during 2mgKOH/g, the Na2CO3 filtering, adding 80 gram 3% washed once, the most again with 100 grams of deionized water wash
Once, then reduce pressure distillation dehydration, i.e. obtains the double triethyl citrate 140g of nylon acyl, yield about 93%.
Being analyzed products therefrom with GC-MS, analysis result is:
Embodiment 3: the preparation of the double tri-iso-butyl citrate of nylon acyl
A) preparation of tri-iso-butyl citrate
Adding 1mol citric acid, 6mol isobutanol, 4.8g aluminium sesquioxide in a kettle., be heated to 160 DEG C, stirring is produced
Raw backflow.After reaction backflow 2 hours, every sampling in 10 minutes once, measure acid number, stop when acid number is less than 5mgKOH/g anti-
Should, under nitrogen atmosphere, normal pressure 115-125 DEG C is distilled off unreacted raw material and by-product, obtains tri-iso-butyl citrate
347g, yield about 96.4%.
B) preparation of nylon anhydride
The preparation of catalyst
Weigh the H of 6g85%3PO4It is dissolved in 20g deionized water, then mixs homogeneously with the HZSM-5 catalyst of 104g, at 55 DEG C
Lower stirring 4 hours, then proceeds to 160 DEG C of oven dryings 4 hours, ground once every 1 hour, breaks into pieces, tabletting after cooling,
Screening 400-600 μm granule, 600 DEG C of roastings 5 hours in Muffle furnace, obtain the modified HZSM-5 type molecular sieve of P, then rise
Warm to 400 DEG C, evacuation in hermetic container, persistently pass to the TiCl that pressure is 3 atmospheric pressure4Steam and N2According to volume ratio
The mixed gas of 1:100, keeps 8 hours, i.e. obtains the double modified HZSM-5 type molecular sieve catalyst of P-Ti, supervises through elementary analysis
Surveying, P content is about 1.3%, TiCl4Content is about 3.02%.
The preparation of nylon anhydride
Weigh nylon acid 150 grams, consist of: succinic acid 30.5%, 1,3-propanedicarboxylic acid 43.2%, adipic acid 26.3%, (nylon acid
Outer purchased from Yancheng Lang De Chemical Company, for GB top grade product, the most aqueous, other impurity contents are less than 1%, ignore not
Meter), modified HZSM-5 type molecular sieve 5g, it is passed through nitrogen, is heated to 280 DEG C, start stirring, and persistently overheating until 320 DEG C, reaction
Stopping heating, cooling after 2.5 hours, filter, crude product is recrystallization in ether, obtains mixture nylon anhydride 119g, receives
Rate is 92%.C) preparation of the double tri-iso-butyl citrate of nylon acyl
Add tri-iso-butyl citrate 300g and nylon anhydride 20g, pyridine 0.6g, XDA-8 macroporous resin in a kettle.
2g, is passed through nitrogen, is warming up to 130 DEG C, starts stirring, every 10 minutes sampling detecting acid numbers after reacting 3 hours, when acid number is less than
Stopped reaction during 2mgKOH/g, cooling, filter, the Na2CO3 solution being subsequently adding 200g1.5% washed once, and adds 150g
Once, then reduce pressure deionized water wash distillation dehydration, obtains the double tri-iso-butyl citrate 305g of product nylon acyl, yield
95%.
Being analyzed products therefrom with GC-MS, result is as follows:
Embodiment 4: plasticizer application Contrast on effect
Conventional plasticizer on double for nylon acyl citrate plasticizers and market is contrasted, the double citrate of nylon acyl
Preparing for embodiment 1-3, other plasticizers used and the equal outsourcing of material, TOTM is tri trimellitate Octyl Nitrite, and DOA is oneself
Adipate, is first according to following formula and makes plastic.Formula forms: PVC powder 100 parts, heat stabilizer 3 parts, plasticising
Agent 50 parts.Each component being sequentially added in 50ml oxolane, stirring to solution is transparent and homogeneous shape, then pours in culture dish quiet
Putting 24h to volatilize completely to solution, obtain transparent PVC thin film, about 1mm is thick.The PVC product that experiment uses prepares the most in this approach.
Table 1 plasticizer key property contrasts
Remarks: 1. detection method performs according to GB/T1669-2001 standard
2. detection method performs according to NF T51-025-1999 standard
3. detection method performs according to standard ASTM D1203-2010
4. according to formula DOP30 part, PVC100 part, heat stabilizer 3 parts is made PVC product, is surveyed its vitrification point, be designated as
T0, constant at other compositions of formula, when plasticizer is changed to variety classes, the vitrification point of PVC product reaches T0Need addition
The number of plasticizer is designated as Wt, Wt/30 and is the plasticizing efficiency of other kind plasticizers, for relative value, the least expression of its numerical value
Plasticizing efficiency is the highest.
Volatile los (air) is the least, and heating loss is the least, illustrates that the stability of plasticizer is the highest；Water sucrose extraction is the least,
Alcohol sucrose extraction is the least, illustrates that the resistance to migration of plasticizer is the best, and the contrast of upper table can be seen that the double citric acid of nylon acyl of the present invention
The stability of ester plasticiser, resistance to migration etc. are superior to conventional products on market.
Embodiment 5: the double citrate Contrast on effect to polylactic acid (PLA) plasticising of nylon acyl
Prepared by poly-lactic acid material: be first dried at 40 DEG C by PLA (mean molecule quantity 137000), then according to 100 parts of PLA ratios
20 parts of plasticizer proportions mix, and compound is extruded through single screw extrusion machine, extrusion temperature one section 130 DEG C, two-stage nitration 140 DEG C, three sections
150 DEG C, the material obtained test mechanical strength, glass transition temperature (Tg), fusing point (Tm) respectively.Result is as shown in the table
PLA plasticization effect is contrasted by the different plasticizer of table 2
Remarks: 1. detection method performs according to standard GB/T 11998-1989
2. detection method performs according to GB/T 7533-1993
3. detection method performs according to standard GB1039
4. detection method performs according to standard GB/T27850-2011 standard
The double citrate plasticizer of nylon acyl of the present invention and conventional citrate plasticizer phase is can be seen that by upper table 2
Ratio, has more preferable mechanical property, it is easier to process and can accelerate the degradation speed of environment-friendly materials, is very suitable for dropping for biology
Solve the plasticising of material.
Claims (19)
1. the preparation method of the double citrate plasticizer of nylon acyl, it is characterised in that the double citrate of described nylon acyl
Mixture for structure below formula:
Wherein, n=2-4, R are the alkyl of C2-C13；
The double citrate of described nylon acyl, with citric acid, monohydric alcohol, nylon acid as raw material, is prepared into by comprising the steps of
Arrive: step 1: the preparation of citrate A:
Citric acid and excess monohydric alcohol react under acidic catalyst is catalyzed, and obtain citrate A；
Step 2: the preparation of nylon anhydride B: nylon acid occurs dehydration to obtain nylon under modified molecular sieve catalyst is catalyzed
Anhydride B；
Step 3: the preparation of the double citrate of nylon acyl: nylon anhydride B and citrate A mixing, at catalyst and promoter effect
Under carry out acylation reaction and obtain the double citrate product of nylon acyl；
Nylon anhydride B catalyst for preparing described in step 2 is the HZSM-5 type molecular sieve that Ti-P is modified.
2. preparation method as claimed in claim 1, it is characterised in that described nylon acid is to produce the by-product of adipic acid,
Comprising adipic acid, succinic acid and 1,3-propanedicarboxylic acid, total amount based on nylon acid, succinic acid content is 15wt%-35wt%, 1,3-propanedicarboxylic acid contains
Amount is 15wt%-35wt% for 40wt%-60wt%, adipic acid content.
3. preparation method as claimed in claim 1, it is characterised in that the monohydric alcohol described in step 1 is ethanol, propanol or straight
One in chain and butanol, amylalcohol, hexanol, enanthol, capryl alcohol, nonyl alcohol, decanol or tridecanol with branched structure；Described lemon
Lemon acid is 1:3-1:15 with the mol ratio of monohydric alcohol, and reaction temperature is 90-160 DEG C.
4. preparation method as claimed in claim 3, it is characterised in that the monohydric alcohol described in step 1 is ethanol, propanol or fourth
One in alcohol, described citric acid is 1:4-1:6 with the mol ratio of monohydric alcohol.
5. preparation method as claimed in claim 1, it is characterised in that the acidic catalyst described in step 1 be sulphuric acid, phosphoric acid,
P-methyl benzenesulfonic acid or solid acid；The consumption of acidic catalyst is the 0.1%-5% of citric acid quality.
6. preparation method as claimed in claim 5, it is characterised in that the acidic catalyst described in step 1 be aluminium sesquioxide,
Antimony oxide, four titanium oxides or four zirconium oxides, the consumption of acidic catalyst is the 1%-2.5% of citric acid quality.
7. the preparation method as according to any one of claim 1-6, it is characterised in that the HZSM-5 type that described Ti-P is modified
The consumption of molecular sieve catalyst is the 1-10% of nylon acid quality；Wherein, total amount based on catalyst, the mass fraction shared by Ti
Mass fraction shared by 1-4%, P is 1-5%.
8. preparation method as claimed in claim 7, it is characterised in that described HZSM-5 type molecule modified for described Ti-P
The consumption of sieve catalyst is the 3-7% of nylon acid quality.
9. preparation method as claimed in claim 7, it is characterised in that the preparation method of the HZSM-5 type molecular sieve that Ti-P is modified
As follows: according to phosphate aqueous solution: HZSM-5 type molecular sieve mass ratio=1:2-1:5 mix homogeneously, at 45 DEG C-60 DEG C, stir 4-
6 hours, then drying and grinding obtained the catalyst precursor particles that particle diameter is 400-600 μm, by catalyst precursor particles roasting
Obtain the modified HZSM-5 type molecular sieve of P；The HZSM-5 type molecular sieve that P is modified is passed to nitrification at 400-500 DEG C
TiCl4Steam, keeps 4-8 hour, i.e. obtains the modified molecular sieve catalyst of Ti-P.
10. preparation method as claimed in claim 9, it is characterised in that the concentration of described phosphate aqueous solution is 10-
30wt%, baking temperature is 130-150 DEG C, and drying time is 3-5 hour, and sintering temperature is 600-700 DEG C, and roasting time is 5-
7 hours.
11. preparation methoies as claimed in claim 7, it is characterised in that the reaction temperature of step 2 dehydration is 200 DEG C-
380 DEG C, the response time is 2-4 hour.
12. preparation methoies as claimed in claim 11, it is characterised in that the reaction temperature of step 2 dehydration is 260 DEG C-
320℃。
13. preparation methoies as claimed in claim 1, it is characterised in that the catalyst of the acylation reaction described in step 3 is to first
Benzenesulfonic acid, pyridine or triethylamine, consumption is the 0.5-2% of nylon anhydride B mass.
14. preparation methoies as claimed in claim 13, it is characterised in that the catalyst of the acylation reaction described in step 3 is Buddhist nun
The 1-1.5% of dragon anhydride B mass.
15. preparation methoies as claimed in claim 1, it is characterised in that the auxiliary agent described in step 3 be macroporous resin XDA-7 or
XDA-8, consumption is the 5%-30% of nylon anhydride B mass.
16. preparation methoies as claimed in claim 15, it is characterised in that the auxiliary dosage described in step 3 is nylon anhydride B matter
The 5%-10% of amount.
17. preparation methoies as claimed in claim 1, it is characterised in that the citrate A described in step 3 and nylon anhydride B's
Mol ratio is 10:1-1:1.
18. preparation methoies as claimed in claim 1, it is characterised in that the citrate A described in step 3 and nylon anhydride B's
Mol ratio is 4:1-2.5:1.
19. preparation methoies as claimed in claim 1, it is characterised in that the reaction temperature of the acylation reaction described in step 3 is
120-155 DEG C, the response time is 2-4 hour.
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| CN106751138B (en) * | 2016-11-24 | 2018-10-16 | 常州大学 | A kind of citrate and the macromolecule of soybean oil synthesis, hyper-branched biomass plasticizer and preparation method thereof |
| CN106633503B (en) * | 2016-11-24 | 2018-10-16 | 常州大学 | A kind of biomass ester derivative and preparation method thereof of epoxidized soybean oil, citrate and dibasic acid anhydride esterification coupling synthesis |
| CN112209913B (en) * | 2020-10-30 | 2021-09-14 | 陕西延长石油（集团）有限责任公司 | Method for preparing adipic anhydride by catalyzing carbonylation of tetrahydrofuran |
| CN115337940B (en) * | 2021-05-14 | 2023-12-15 | 江苏理工学院 | Preparation method and application of catalyst for synthesizing triisobutyl citrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3239555A (en) * | 1960-12-09 | 1966-03-08 | Benckiser Gmbh Joh A | Bis-citric acid esters |
| CN102226013A (en) * | 2011-05-05 | 2011-10-26 | 浙江建业化工股份有限公司 | Method for producing cold-resistant plasticizer through by-product nylon acids |
| CN103113617A (en) * | 2013-02-06 | 2013-05-22 | 山东万图高分子材料有限公司 | Novel plasticizer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3239555A (en) * | 1960-12-09 | 1966-03-08 | Benckiser Gmbh Joh A | Bis-citric acid esters |
| CN102226013A (en) * | 2011-05-05 | 2011-10-26 | 浙江建业化工股份有限公司 | Method for producing cold-resistant plasticizer through by-product nylon acids |
| CN103113617A (en) * | 2013-02-06 | 2013-05-22 | 山东万图高分子材料有限公司 | Novel plasticizer and preparation method thereof |
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