CN108047153A - A kind of annular carbodiimides of low volatilization and preparation method thereof - Google Patents
A kind of annular carbodiimides of low volatilization and preparation method thereof Download PDFInfo
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- CN108047153A CN108047153A CN201711382817.XA CN201711382817A CN108047153A CN 108047153 A CN108047153 A CN 108047153A CN 201711382817 A CN201711382817 A CN 201711382817A CN 108047153 A CN108047153 A CN 108047153A
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- carbodiimides
- annular
- low
- volatilization
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/10—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The present invention is using the raw material being easy to get,Low volatility ring-type carbodiimides (I) are prepared by solvent-free polycondensation reaction,Molecular weight is 500~1300 (in terms of number-average molecular weights),Molecular weight is moderate,Active constituent content is high,Be easy to uniformly make an addition in high molecular material and it is not easy to migrate or effusion,Melting range is 70~140 DEG C,Finished product structure symmetry is good,And without soft segment,Easily by crystallization and purification,Yield is high,Solid forms are conveniently used for process operation,Improve the hydrolytic Resistance of polyester material,And volatile materials will not be generated during processing use,Safety and environmental protection,It can make resistant to hydrolysis stabilization and be widely used in polyesters,Polyurethanes,Ethylene-vinyl acetate resin,Biodegradation material,The production and processing of the polymer materials such as nylon,Delay the hydrolysis of material,Prolong the service life.
Description
Technical field
The present invention relates to a kind of carbodiimides and preparation method thereof more particularly to a kind of annular carbon of low volatilization
Change diimine class compound and preparation method thereof, stabilisers against hydrolysis can be used as polyesters (PET, PBT, PC), polyurethane
Class (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..Polyester
Material has a variety of excellent performances, is widely used in modern society, wherein, PET has good fibre forming property, wearability, anti-compacted
Denaturation 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 material
The mechanical properties such as material surface smoothness, intensity, hardness, elasticity all bring very big negative effect.Such issues that most economical solution
Method be addition Carbodiimides anti-hydrolysis agent, carbodiimides can with polyester material decompose generate carboxylic acid or
Water 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 material
Service 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 used
Easy xanthochromia, use scope are limited in journey.The easily stored transport of aromatic series carbodiimides, and it is relatively stable and wide under room temperature
General 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 west
Stabilizer 7000 of lattice etc., for example bright Stabaxol P for containing chemistry of aggretion type carbodiimides, La Xige's
Stabilizer 9000 etc..
Carbodiimides on the market can delay the needs that polyester material hydrolyzes in satisfaction to a certain degree, but
There is also fault of construction problems, these common Carbodiimides products are mostly linear structure, during production and application, especially
Volatile isocyanate ester compound is also easy to produce during its high temperature process, smell is severe, pollutes environment, and harm health has peace
Full hidden danger.
To solve the above problems, market survey emphasis turns to new structure carbodiimides, lacked to develop without structure
Sunken 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 material
With 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 two
Imine 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 liquid
It reacting in body medium, reaction temperature is -20~30 DEG C, obtains 4,4 ',-diisocyanate -3,3 ', 5,5 '-tetraalkyl is adjacent
Terphenyl, 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 catalysts
Effect carries out condensation reaction, interior when 5~10 is small to prepare annular carbodiimides crude product, detects no isocyano
I.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 white
Color 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 heptan
Alkane.4,4 ',-diamino -3,3 ', 5,5 '-tetraalkyl ortho-terphenyl, two (trichloromethyl) carbonic esters, the matter of inert liquid medium
Amount 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 penta
One or more in alkene -1- oxides and its isomers, one kind in 1- methyl-1s-oxygen-Phospholes and its isomers
It 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 molten
The mass ratio of agent and annular carbodiimides crude product is 1.5~5:1；Crystallization temperature is -20~30 DEG C, crystallization time
For 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 weight
Meter), 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 range
For 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 reaction
Carbodiimides, finished product structure symmetry is good, and is free of soft segment, easily by crystallization and purification, and yield is high, solid forms
Process operation is conveniently used for, improves the hydrolytic Resistance of polyester material, and processes use to generate volatility in the process
Substance, 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. 1
Shown 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. 2
It is shown.
Specific embodiment：
To further understand the present invention, with reference to embodiment to annular carbodiimides provided by the present invention and its system
Preparation 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- first
Base -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, test
Up 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 powder
End, 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 and
6.96 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 18
Hour, 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, continues
6h 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 carbodiimides
White 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 and
3.86 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 until
No isocyano residual, cools to 80 DEG C, adds in 20kg butyronitrile stirring 30min, is cooled to 20 DEG C, continue to stir 4h, generates big
White 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% ratio
In sour glycol ester, prepare dumbbell shaped tensile bars, together with blank batten 120 DEG C, 101MPa, saturated vapor condition
Under 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 tensilon
Show.From the figure, it can be seen that the tensile strength of blank PET declines substantially than annular carbodiimides chemical combination in addition embodiment 3
The 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 exists
270-310℃.Master batch after granulation takes 50g samples respectively, small-molecule substance therein is separated by dissolving-precipitation method, with height
The 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 1
Sharp 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 equivalent
1, embodiment 2, carbodiimides and commercial carbonized diimine (4#) (Stabaxol I, Rhein) master batch synthesized by embodiment 3
Under 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 bright
Aobvious sharp aroma, embodiment 1, embodiment 2, the basic insipidness of carbodiimides synthesized by embodiment 3.
Claims (10)
1. a kind of annular carbodiimides of low volatilization, it is characterised in that：With following general structure (I)：
Wherein, R1、R2、R3、R4=hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, phenoxy group.
A kind of 2. method for preparing the annular carbodiimides of low volatilization described in claim 1, it is characterised in that bag
Include following steps：
(1) 4,4 '-diamino -3,3 ', 5,5 '-tetraalkyl ortho-terphenyl and two (trichloromethyl) carbonic esters are in inert liquid medium
In react, reaction temperature is -20~30 DEG C, obtains 4,4 '-diisocyanate -3,3 ', 5,5 '-tetraalkyl ortho-terphenyl,
Reaction equation is：
Wherein, X is Na or K.
(2) 4,4 '-diisocyanate -3,3 ', 5,5 '-tetraalkyl ortho-terphenyl at a certain temperature through phosphorus series catalysts act on into
Row condensation reaction, it is interior when 5~10 is small to prepare annular carbodiimides crude product, it detects and is remained without no isocyano
I.e. reaction was completed.80 DEG C are cooled to, adds in purification solvent, cooling recrystallization filters, leaves and takes filter cake, and white crystalline substance is obtained after drying
Body ring-type carbodiimides (I), reaction equation are：
Wherein, R1、R2、R3、R4=hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, phenoxy group.
3. a kind of the low annular carbodiimides of volatilization described in claim 1 are prepared according to claim 2
Method, it is characterised in that：(1) the 4,4 '-diamino -3,3 ' of step, 5,5 '-tetraalkyl ortho-terphenyl, two (three chloromethanes
Base) carbonic ester, inert liquid medium mass ratio be 1:2~20:1~500.
4. a kind of the low annular carbodiimides of volatilization described in claim 1 are prepared according to claim 2
Method, it is characterised in that：Step (1) inert liquid medium is toluene, dimethylbenzene, methane, halide, ethane, halogen
For ethane, normal heptane.
5. a kind of the low annular carbodiimides of volatilization described in claim 1 are prepared according to claim 2
Method, it is characterised in that：Step (2) condensation temp is 80~230 DEG C.
6. a kind of the low annular carbodiimides of volatilization described in claim 1 are prepared according to claim 2
Method, it is characterised in that：Step (2) the phosphorus series catalysts and 4,4 '-diisocyanate -3,3 ', 5,5 '-tetraalkyl neighbour three
The mass ratio of biphenyl is 3 × 10-5~8 × 10-3:1。
7. a kind of the low annular carbodiimides of volatilization described in claim 1 are prepared according to claim 2
Method, it is characterised in that：Step (2) the phosphorus series catalysts for 3- methyl-1s-phenyl -2- Phospholes -1- oxides,
One or more in 1- methyl-1s-oxygen-Phospholes and its isomers.
8. a kind of the low annular carbodiimides of volatilization described in claim 1 are prepared according to claim 2
Method, it is characterised in that：The step (2) purifies solvent and the mass ratio of annular carbodiimides crude product is
1.5~5:1.
9. the low annular carbodiimides that volatilize of one kind according to claim 1, it is characterised in that：It is described low to wave
Hair property ring-type carbodiimides molecular weight is 500~1300 (in terms of number-average molecular weights), and melting range is 70~140 DEG C.
10. the low annular carbodiimides that volatilize of one kind according to claim 1, it is characterised in that：It is described low
The weight content that volatile cyclic carbodiimides add in high molecular material is 0.05~10%.
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| CN201711382817.XA CN108047153A (en) | 2017-12-20 | 2017-12-20 | A kind of annular carbodiimides of low volatilization and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317526A (en) * | 2019-06-28 | 2019-10-11 | 广东华江粉末科技有限公司 | A kind of high resistance to infiltration powdery paints and preparation method thereof |
| CN111471282A (en) * | 2019-01-23 | 2020-07-31 | 朗盛德国有限责任公司 | Composition comprising polyethylene terephthalate and at least one monomeric carbodiimide, method for the production thereof and use thereof |
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| CN1585764A (en) * | 2001-11-09 | 2005-02-23 | 百奥塔科学管理有限公司 | Dimeric compounds and their use as anti-viral agents |
| US20080161554A1 (en) * | 2006-12-28 | 2008-07-03 | Great Eastern Resins Industrial Co., Ltd. | Macrocyclic carbodiimides (MC-CDI) and their derivatives, syntheses and applications of the same |
| CN103936954A (en) * | 2014-04-21 | 2014-07-23 | 上海朗亿功能材料有限公司 | Novel polycarbodiimide compound and preparation method thereof |
| CN106810506A (en) * | 2015-11-27 | 2017-06-09 | 上海朗亿功能材料有限公司 | A kind of novel cyclic bi-carbodiimide compound and preparation method thereof |
-
2017
- 2017-12-20 CN CN201711382817.XA patent/CN108047153A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585764A (en) * | 2001-11-09 | 2005-02-23 | 百奥塔科学管理有限公司 | Dimeric compounds and their use as anti-viral agents |
| US20080161554A1 (en) * | 2006-12-28 | 2008-07-03 | Great Eastern Resins Industrial Co., Ltd. | Macrocyclic carbodiimides (MC-CDI) and their derivatives, syntheses and applications of the same |
| CN103936954A (en) * | 2014-04-21 | 2014-07-23 | 上海朗亿功能材料有限公司 | Novel polycarbodiimide compound and preparation method thereof |
| CN106810506A (en) * | 2015-11-27 | 2017-06-09 | 上海朗亿功能材料有限公司 | A kind of novel cyclic bi-carbodiimide compound and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471282A (en) * | 2019-01-23 | 2020-07-31 | 朗盛德国有限责任公司 | Composition comprising polyethylene terephthalate and at least one monomeric carbodiimide, method for the production thereof and use thereof |
| CN110317526A (en) * | 2019-06-28 | 2019-10-11 | 广东华江粉末科技有限公司 | A kind of high resistance to infiltration powdery paints and preparation method thereof |
| CN110317526B (en) * | 2019-06-28 | 2021-08-03 | 广东华江粉末科技有限公司 | High-water-seepage-resistance powder coating and preparation method thereof |
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