A kind of annular carbodiimides of low volatilization and preparation method thereofTechnical field
The present invention relates to a kind of carbodiimides and preparation method thereof more particularly to a kind of annular carbon of low volatilizationChange diimine class compound and preparation method thereof, stabilisers against hydrolysis can be used as polyesters (PET, PBT, PC), polyurethaneClass (PU, TPU, CPU, PU adhesive, coating etc.), ethylene-vinyl acetate resin (EVA), biodegradation material (PLA,PBAT), the production and processing of the polymer materials such as nylon (PA66, PA6) extends the service life of material.
Background technology
Polyester material is polymer, such as PET obtained by polyalcohol and polyacid polycondensation, PBT, PU, PLA, PBAT etc..PolyesterMaterial has a variety of excellent performances, is widely used in modern society, wherein, PET has good fibre forming property, wearability, anti-compactedDenaturation and electrical insulating property etc.；PU materials oil resistant, wear-resisting, intensity is high；PLA, PBAT material safety and environmental protection, degradable green, still,Polyester material is there are one weakness, and in a humidity environment, particularly the condition of high temperature, ester bond easily hydrolyze, and hydrolysis phenomena is to materialThe mechanical properties such as material surface smoothness, intensity, hardness, elasticity all bring very big negative effect.Such issues that most economical solutionMethod be addition Carbodiimides anti-hydrolysis agent, carbodiimides can with polyester material decompose generate carboxylic acid orWater reacts, and generates the stable urea-based compound being free from side effects, and delays the further progress of hydrolysis, so as to improve polyester materialService life.
Carbodiimides can be divided into aliphatic carbodiimides and aromatic series carbodiimides, and wherein aliphatic carbonization two is sub-Amine is usually liquid, and aromatic series carbodiimides is normally solid, and aliphatic carbodiimides are relatively unstable, and storage usedEasy xanthochromia, use scope are limited in journey.The easily stored transport of aromatic series carbodiimides, and it is relatively stable and wide under room temperatureGeneral application.Aromatic series carbodiimides include single second carbide imine, more carbodiimides, polycarbodiimide class,Industrially widely applied is single second carbide imine class anti-hydrolysis agent, the bright Stabaxol I for containing chemistry of such as Germany, German to draw westStabilizer 7000 of lattice etc., for example bright Stabaxol P for containing chemistry of aggretion type carbodiimides, La Xige'sStabilizer 9000 etc..
Carbodiimides on the market can delay the needs that polyester material hydrolyzes in satisfaction to a certain degree, butThere is also fault of construction problems, these common Carbodiimides products are mostly linear structure, during production and application, especiallyVolatile isocyanate ester compound is also easy to produce during its high temperature process, smell is severe, pollutes environment, and harm health has peaceFull hidden danger.
To solve the above problems, market survey emphasis turns to new structure carbodiimides, lacked to develop without structureSunken Carbodiimides product.It is complicated that a kind of raw material is disclosed in the patent of Publication No. CN106810506A, by sulfonation,It is good that numerous cumbersome steps such as substitution are prepared a kind of resistant to hydrolysis effect, and with chain extension effect, improves making for polyester materialWith the annular bi-carbodiimide compound in service life.
In conclusion environment-friendly and high-performance, high temperature working processes are not volatile, and raw material is easy to get, and prepare simple carbonization twoImine compound has a vast market prospect.
The content of the invention
The present invention provides a kind of low volatility ring-type carbodiimides and preparation method thereof, it is characterised in that,With following general structure (I)：
Wherein, R1、R2、R3、R4=hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, phenoxy group.
The preparation method of the annular carbodiimides (I) of the present invention：
(1) 4,4 ',-diamino -3,3 ', 5,5 '-tetraalkyl ortho-terphenyl and two (trichloromethyl) carbonic esters are in inert liquidIt reacting in body medium, reaction temperature is -20~30 DEG C, obtains 4,4 ',-diisocyanate -3,3 ', 5,5 '-tetraalkyl is adjacentTerphenyl, reaction equation are：
Wherein, X is Na or K.
(2) 4,4 ',-diisocyanate -3,3 ', 5,5 '-tetraalkyl ortho-terphenyl is at a certain temperature through phosphorus series catalystsEffect carries out condensation reaction, interior when 5~10 is small to prepare annular carbodiimides crude product, detects no isocyanoI.e. reaction was completed for residual.80 DEG C are cooled to, adds in purification solvent, cooling recrystallization filters, leaves and takes filter cake, obtained after drying whiteColor crystal ring-type carbodiimides (I), reaction equation are：
Wherein, R1、R2、R3、R4=hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, phenoxy group.
Step (1) described inert liquid medium is toluene, dimethylbenzene, methane, halide, ethane, halothane, positive heptanAlkane.4,4 ',-diamino -3,3 ', 5,5 '-tetraalkyl ortho-terphenyl, two (trichloromethyl) carbonic esters, the matter of inert liquid mediumAmount is than being 1:2~20:1~500.
Step (2) described condensation reaction be solvent-free polycondensation reaction, condensation temp be 80~230 DEG C, preferably 100~200℃。
Step (2) the phosphorus series catalysts often sell phosphorus series catalysts for market, such as 3- methyl-1s-phenyl -2- phosphorus heterocycles pentaOne or more in alkene -1- oxides and its isomers, one kind in 1- methyl-1s-oxygen-Phospholes and its isomersIt is or a variety of.The phosphorus series catalysts and 4,4 ',-diisocyanate -3,3 ', the mass ratio of 5,5 '-tetraalkyl ortho-terphenyl is 3×10-5~8 × 10-3:1。
Step (2) the purification solvent is ethyl alcohol, methanol, isopropanol, n-butanol, acetone, butyronitrile, petroleum ether；It purifies moltenThe mass ratio of agent and annular carbodiimides crude product is 1.5~5:1；Crystallization temperature is -20~30 DEG C, crystallization timeFor 2~for 24 hours.
The weight content that the low volatility ring-type carbodiimides add in high molecular material is 0.05~10%.
The molecular weight of low volatility ring-type carbodiimides prepared by the present invention is for 500~1300 (with number-average molecular weightMeter), molecular weight is moderate, and active constituent content is high, is easy to uniformly make an addition in high molecular material and not easy to migrate or effusion, melting rangeFor 70~140 DEG C, low volatility ring-type carbodiimides structure of the invention is more symmetrical in addition, more rigid,It is not easily decomposed, product is not volatile, can make resistant to hydrolysis stabilization and be widely used in polyesters (PET, PBT, PC), polyurethanes(PU, TPU, CPU, PU adhesive, coating etc.), ethylene-vinyl acetate resin (EVA), biodegradation material (PLA,PBAT), the production and processing of the polymer materials such as nylon (PA66, PA6), delays the hydrolysis of material, prolongs the service life.
It is raw materials used in the present invention to be easy to get or easily prepare, low volatility ring-type is prepared by solvent-free polycondensation reactionCarbodiimides, finished product structure symmetry is good, and is free of soft segment, easily by crystallization and purification, and yield is high, solid formsProcess operation is conveniently used for, improves the hydrolytic Resistance of polyester material, and processes use to generate volatility in the processSubstance, safety and environmental protection, use easy to spread.
Description of the drawings：
Fig. 1 Fig. 1 is I -1 nuclear magnetic resonance map in deuterochloroform of products therefrom in embodiment 1, each peak ownership such as Fig. 1Shown in.
Fig. 2 Fig. 2 is the tensile strength test chart for being with the addition of 1 product of embodiment, I -1 post-tensioning batten, test result such as Fig. 2It is shown.
Specific embodiment：
To further understand the present invention, with reference to embodiment to annular carbodiimides provided by the present invention and its systemPreparation Method illustrates, but protection scope of the present invention should not be limited by the examples.
Embodiment 1
Under nitrogen protection, 6.24 kilogram 4,4 ',-diisocyanate -3,3 ', 5,5 ' ortho-terphenyls and 1.872 grams of 3- firstBase -1- phenyl -2- Phospholes -1- oxides are added in reaction kettle, be heated to 130 DEG C be stirred to react 15 it is small when, testUp to no isocyano residual, 80 DEG C are cooled to, 10kg isopropanols stirring 30min is added in, is cooled to 20 DEG C, continue to stir 4h,A large amount of white powder crystallizations are generated, filters, is put into 40 DEG C of dryings of baking oven, obtain 5.07 kilograms of annular carbodiimides white powderEnd, fusing point are 82 DEG C, molecular weight 537, yield 94.4%.
Embodiment 2
Under nitrogen protection, 10.74 kilogram 4,4 ',-diisocyanate -3,3 ', 5,5 '-tetra-n-butyl ortho-terphenyl and6.96 grams of 3- methyl-1s-phenyl -2- Phospholes -1- oxides are added in reaction kettle, are heated to 150 DEG C and are stirred to react 18Hour, test is remained up to no isocyano, cools to 90 DEG C, is added in 20kg ethyl alcohol stirring 30min, is cooled to 20 DEG C, continues6h is stirred, a large amount of white powder crystallizations is generated, filters, be put into 40 DEG C of dryings of baking oven, obtains 9.28 kilograms of annular carbodiimidesWhite powder, fusing point are 97 DEG C, molecular weight 986, yield 94.1%.
Embodiment 3
Under argon gas protection, 9.62 kilogram 4,4 ',-diisocyanate -3,3 ', 5,5 '-tetra isopropyl ortho-terphenyl and3.86 grams of 1- methyl-1s-oxygen-Phospholes are added in reaction kettle, be heated to 180 DEG C be stirred to react 10 it is small when, test untilNo isocyano residual, cools to 80 DEG C, adds in 20kg butyronitrile stirring 30min, is cooled to 20 DEG C, continue to stir 4h, generates bigWhite powder crystallization is measured, filters, is put into 40 DEG C of dryings of baking oven, obtains 8.44 kilograms of annular carbodiimides (I-1) white powders,Fusing point is 95 DEG C, molecular weight 873, yield 96.7%.
Cyclic carbodiimide compounds (I-1) synthesized in embodiment 3 are added in into terephthaldehyde with 0.8% ratioIn sour glycol ester, prepare dumbbell shaped tensile bars, together with blank batten 120 DEG C, 101MPa, saturated vapor conditionUnder ageing oven in tested, then test the mechanical performance of each batten.
Tensile strength test, test result such as 2 institute of attached drawing are carried out to the batten of different ageing times using tensilonShow.From the figure, it can be seen that the tensile strength of blank PET declines substantially than annular carbodiimides chemical combination in addition embodiment 3The batten of object is fast, illustrates that the batten hydrolytic Resistance for adding cyclic carbodiimide compounds in embodiment 3 is better than blank PET.
By embodiment 1, embodiment 2, carbodiimides and commercial carbonized diimine (4#) synthesized by embodiment 3(Stabaxol I, Rhein) is mixed into the ratio of 2wt% in PET respectively, is granulated and is squeezed out through 35 machines, wherein, processing temperature exists270-310℃.Master batch after granulation takes 50g samples respectively, small-molecule substance therein is separated by dissolving-precipitation method, with heightThe content of effect liquid phase chromatogram (HPLC) quantitative analysis wherein isocyanates is as a result as follows：
1 isocyanate content of table tests table
| Group | HPLC (units：ppm) |
| Embodiment 1 | 525 |
| Embodiment 2 | 500 |
| Embodiment 3 | 448 |
| 4# | 2600 |
It can be seen that, the content of the isocyanates of commercial carbonized diimine (4#) is 2600ppm, and about this is special from table 1Sharp embodiment 1, embodiment 2,5 times or more of embodiment 3.Illustrate the product compared to commercial like product, synthesized through this patent,The volatility of high-temperature heating process substantially reduces.
In addition, with reference to the smell identification method [with reference to masses PV3900 (2000)] of automobile industry, by the embodiment of equivalent1, embodiment 2, carbodiimides and commercial carbonized diimine (4#) (Stabaxol I, Rhein) master batch synthesized by embodiment 3Under conditions of being placed in 240 DEG C closing heating after ten minutes, open bottle cap, the results show that commercial carbonized diimine (4#) also have it is brightAobvious sharp aroma, embodiment 1, embodiment 2, the basic insipidness of carbodiimides synthesized by embodiment 3.