CN108203418A - A kind of epoxy-modified single second carbide imine class compound and preparation method thereof - Google Patents
A kind of epoxy-modified single second carbide imine class compound and preparation method thereof Download PDFInfo
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- CN108203418A CN108203418A CN201611185814.2A CN201611185814A CN108203418A CN 108203418 A CN108203418 A CN 108203418A CN 201611185814 A CN201611185814 A CN 201611185814A CN 108203418 A CN108203418 A CN 108203418A
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- carbide imine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of epoxy-modified single second carbide imine class compounds and preparation method thereof.Epoxy-modified single second carbide imine class compound purity prepared by the present invention is high, fusing point is at 70 120 DEG C, it is not only a kind of excellent stabilisers against hydrolysis, it is also a kind of excellent chain extender, polyester material is effectively prevent to hydrolyze, repairs polyester material segment, improves the stability in polyester material process, it solves the problems, such as that carbodiimides volatilizees and generates smell in process, has also thoroughly prevented the hidden danger of migration.The preparation process of the epoxy-modified single second carbide imine class compound includes：(1) bromination reaction；(2) substitution reaction；(3) it is epoxy-modified.
Description
Technical field
The present invention relates to a kind of carbodiimides more particularly to a kind of epoxy-modified single second carbide imine classes
Close object.
Background technology
Carbodiimides are excellent stabilisers against hydrolysis, and the high molecular material containing ester group is by water or acid attack
When, the ester bond in molecule is cracked into alcohol and acid, and acid can be such that hydrolysis rate exponentially rises again, Carbodiimides chemical combination
Object can capture this free carboxy acid, the stable uride of fast reaction generation under room temperature, prevent hydrolysis further deeply, so as to carry
The hydrolytic stability of high high molecular material.
Carbodiimides include single second carbide imine, more carbodiimides, polycarbodiimide class compound.
Widely applied mostly single second carbide imine class anti-hydrolysis agent industrial at present, the bright chemistry (i.e. Rhein is chemical) of containing of such as Germany are released
Stabaxol series anti-hydrolysis agents, German Stabilizer series anti-hydrolysis agent etc..This kind of anti-hydrolysis agent purity is high, is easy to make
Standby but molecular weight is less than normal, melts low boiling point, is easy to external migration so as to reduce make from polyester, polyurethanes compound under high temperature
With effect, it is impossible to improve the long-term hydrolytic stability of material well.To solve problems, market survey hot spot turns to
Seek the single second carbide imine class compound of high molecular weight, it is desirable to the fusing point of Carbodiimides is improved with this.
Invention content
The present invention connects epoxy group, one kind is prepared in the molecule both ends of monomer carbodiimides, further synthesis
Dystectic epoxy-modified single second carbide imine class compound.
A kind of epoxy-modified single second carbide imine class compound, has the following structure general formula (I)：
Wherein, R1、R2、R3、R4=hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, phenoxy group.
A kind of preparation of epoxy-modified single second carbide imine class compound (I) includes the following steps：
(1) bromination reaction：In organic solvent, N, N ' -2,2 ', 6,6 '-tetraalkyl phenyl single second carbide imine and bromine water
Addition reaction is carried out at a certain temperature, adjusts pH value to 7 with lye, it is sub- that bromo single carbonization two was prepared in 6~10 hours
Amine suspension；
(2) substitution reaction：Lye, bisphenol-A, reflux water-dividing are added in into the suspension.Organic phase through 10% alkali liquid washing,
Solvent is evaporated off after desiccant dryness, obtains intermediate bisphenol-A for single second carbide imine；
(3) it is epoxy-modified：To above-mentioned intermediate double phenol A for epoxychloropropane is added in single second carbide imine, lye is added in,
Heating 4-5 hours, and washed with ethyl alcohol, obtain the epoxy-modified single second carbide imine of final products.
Wherein, R1、R2、R3、R4、R5=hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, phenoxy group.
Step (1) organic solvent for toluene, dimethylbenzene, dichloroethanes, dichloromethane, petroleum ether, acetone, butanone,
Chloroform, DMF, chloropropane, ethyl acetate etc.；Addition reaction temperature is -10-10 DEG C；
Step (2) reflux temperature is 40~180 DEG C, and drier is anhydrous sodium sulfate, anhydrous magnesium sulfate.
The step (1), (2), (3) lye for sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, carbon
Potassium hydrogen phthalate etc..
The N, N ' -2,2 ', 6,6 '-tetraalkyl phenyl single second carbide imine and bromine water, bisphenol-A, epoxychloropropane rub
That equivalent proportion position 1:1.05~1.3:1.8~2:1.5~2.
The yield of the bromo single second carbide imine is 93%.The bisphenol-A is 87% for the yield of single second carbide imine.
The yield of the epoxy-modified single second carbide imine is 95%.
Monomer carbodiimides purity prepared by the present invention is high, and fusing point improves steady in process at 70-120 DEG C
It is qualitative.Epoxy group in structure of the present invention can be reacted with the hydroxyl isoreactivity group in polyester or polyurethane, not only be played
It is crosslinked the effect of chain extension, moreover it is possible to carbodiimides be connected on the segment of polyester or polyurethane material, effectively prevent polyester material
The segment of polyester material is repaired in the hydrolysis of material, improves the performance of material, is solved carbodiimides in process and is volatilized and generate
The problem of smell, has also thoroughly prevented the hidden danger of migration.The epoxy-modified single second carbide imine that the present invention is prepared is not still
A kind of excellent stabilisers against hydrolysis and a kind of excellent chain extender.
Description of the drawings
Fig. 1.Fig. 1 is blank PET, the epoxy-modified single second carbide imine (product A) of addition, adds commercially available single second carbide imine
The PET batten hydrolytic Resistance contrast test figures of (product B), test result are as shown in Figure 1.
Specific embodiment
Embodiment 1
(1) in 100ml toluene, addition 25g (quality) N, N ' -2,2 ', 6,6 '-tetramethylphenyl single second carbide imine,
The toluene solution (brominated 17g) of agitation and dropping 100g (quality) bromine under the conditions of -5 DEG C carries out after being added dropwise to complete 5 DEG C (temperature)
Addition reaction 2h, then pH value is adjusted to 7 with saturation sodium hydroxide solution, continue to be stirred to react 4-6 hours and prepare bromo single carbon
Change diimine suspension, analyzed every 1h samplings HPLC, N, N ' -2,2 ', 6,6 '-tetramethylphenyl single second carbide imine content is low
It is completed in 0.5% for reaction；
(2) 20ml sodium hydroxide solutions are added in into the suspension, the toluene solution 100ml of bisphenol-A is added dropwise (containing bis-phenol
A43g), 110 DEG C of reflux water-dividing 5h.Organic phase is washed through 10% sodium carbonate liquor, and anhydrous sodium sulfate drying is evaporated off solvent, obtains
37g intermediate bisphenol-As are for single second carbide imine；
(3) it is stirred molten to above-mentioned intermediate double phenol A for 100g acetone, 15g epoxychloropropane is added in single second carbide imine
Solution is warming up to 50 DEG C, and 10% lye 30ml is added dropwise, and reacts 4-5 hours.Every 1h sampling HPLC analyses, until intermediates content is low
In 0.5%.Liquid separation, washing is primary, and solvent is evaporated off, and with methanol crystallization, methanol washing filters, dry, obtains 60g white powders
Epoxy-modified single second carbide imine, 73 DEG C of fusing point.
Embodiment 2
(1) in 100ml dimethylbenzene, addition 36g (quality) N, N ' -2,2 ', 6,6 '-tetra isopropyl phenyl single carbonization two is sub-
Amine, the xylene solution (brominated 17g) of agitation and dropping 100g (quality) bromine under the conditions of -5 DEG C, in 5 DEG C of (temperature after being added dropwise to complete
Degree) addition reaction 3h is carried out, then pH value is adjusted to 7 with saturated sodium carbonate solution, continue to be stirred to react 4-7 hours and prepare bromo
Single second carbide imine suspension；Every 1h sampling HPLC analyses, N, N ' -2,2 ', 6,6 '-tetra isopropyl phenyl single second carbide imine
Content is completed less than 0.5% for reaction；
(2) 30ml saturated solution of sodium carbonate is added in into the suspension, the xylene solution 100ml of bisphenol-A is added dropwise (containing double
Phenol A44g), 140 DEG C of reflux water-dividings.Organic phase is washed through 10% sodium hydroxide solution, is obtained among 64g after anhydrous sodium sulfate drying
Body bisphenol-A is for single second carbide imine；
(3) it is stirred to above-mentioned intermediate double phenol A for 100g petroleum ethers, 16g epoxychloropropane is added in single second carbide imine
Dissolving is warming up to 50 DEG C, and 10% sodium hydroxide solution 30ml is added dropwise, and reacts 4-7 hours.Every 1h sampling HPLC analyses, until in
Mesosome content is less than 0.5%.Liquid separation, washing is primary, and solvent is evaporated off, and with alcohol crystal, ethyl alcohol washing filters, dry, obtains 67g
The epoxy-modified single second carbide imine of white powder.80 DEG C of fusing point.
Embodiment 3
(1) in 100ml chloropropanes, addition 25g (quality) N, N ' -2,2 ', 6,6 '-tetrabutyl phenyl single second carbide imine
The toluene solution (brominated 18g) of agitation and dropping 100g (quality) bromine under the conditions of -5 DEG C carries out after being added dropwise to complete 5 DEG C (temperature)
Addition reaction 2h, then pH value is adjusted to 7 with saturation sodium hydroxide solution, continue to be stirred to react 4-10 hours and prepare bromo single carbon
Change diimine suspension, analyzed every 1h samplings HPLC, N, N ' -2,2 ', 6,6 '-tetrabutyl phenyl single second carbide imine content is low
It is completed in 0.5% for reaction；；
(2) 25ml saturated solution of sodium carbonate is added in into the suspension, the chloropropane solution 100ml of bisphenol-A is added dropwise (containing double
Phenol A43g), 140 DEG C of reflux water-dividings.Organic phase is washed through 10% sodium hydroxide solution, is obtained among 72g after anhydrous sodium sulfate drying
Body bisphenol-A is for single second carbide imine；
(3) it is stirred molten to above-mentioned intermediate double phenol A for 200g acetone, 16g epoxychloropropane is added in single second carbide imine
Solution is warming up to 50 DEG C, and 10% sodium hydroxide solution 30ml is added dropwise, and reacts 4-7 hours.Every 1h sampling HPLC analyses, until intermediate
Body content is less than 0.5%.Liquid separation, washing is primary, and solvent is evaporated off, and with alcohol crystal, methanol washing filters, dry, and it is micro- to obtain 74g
The epoxy-modified single second carbide imine of yellow powder, 116 DEG C of fusing point.
By the epoxy-modified single second carbide imine (product A) synthesized in embodiment 3, commercially available single second carbide imine (product B)
It is added in ethylene glycol terephthalate (PET) with 2% ratio respectively, prepares dumbbell shaped tensile bars, by the batten and sky
White PET battens carry out contrast test in the ageing oven under the conditions of 120 DEG C, 101MPa, saturated vapor, are surveyed in different time
The tensile strength of each batten is tried, test result is as shown in Figure 1.
From the figure, it can be seen that the PET battens tensile strength for not adding single second carbide imine declines apparent, hydrolytic resistance
It can be very poor.After adding single second carbide imine class product, hydrolytic Resistance is greatly improved.After 3 hours, addition epoxy changes
Property single second carbide imine (product A) and the commercially available single second carbide imine (product B) of addition PET battens tensile strength respectively about
50Mpa、30Mpa.After 4 hours, add epoxy-modified single second carbide imine (product A) and the commercially available single carbonization two of addition is sub-
The PET battens tensile strength of amine (product B) about 40Mpa, 20Mpa respectively.Epoxy group in product A of the present invention can in PET
Hydroxyl isoreactivity group reaction, not only play the role of be crosslinked chain extension, moreover it is possible to carbodiimides is connected to the segment of PET material
On, the hydrolysis of PET material is effectively prevent, repairs the segment of PET material, improves the performance of material, so adding epoxy-modified list
Carbodiimides (product A) is longer than the PET batten resistant to hydrolysis times for adding commercially available single second carbide imine (product B), and performance is more
It is excellent.
Claims (9)
1. a kind of epoxy-modified single second carbide imine class compound, it is characterised in that structural formula is as follows：
Wherein, R1、R2、R3、R4=hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, phenoxy group.
A kind of 2. method for preparing epoxy-modified single second carbide imine class compound described in claim 1, it is characterised in that packet
Include following steps：
(1) bromination reaction：In organic solvent, N, N ' -2,2 ', 6,6 '-tetraalkyl phenyl single second carbide imine is with bromine water one
Determine to carry out addition reaction at temperature, adjust pH value to 7 with lye, bromo single second carbide imine was prepared in 6~10 hours and is hanged
Supernatant liquid；
(2) substitution reaction：Lye, bisphenol-A, reflux water-dividing are added in into the suspension.Organic phase is dry through 10% alkali liquid washing
Solvent is evaporated off after agent drying, obtains intermediate bisphenol-A for single second carbide imine；
(3) it is epoxy-modified：To above-mentioned intermediate double phenol A for epoxychloropropane is added in single second carbide imine, lye, heating are added in
4-5 hours.And washed with ethyl alcohol, obtain the epoxy-modified single second carbide imine of final products.
Reaction equation is as follows：
3. a kind of method for preparing epoxy-modified single second carbide imine class compound according to claim 2, feature exist
In the step (1) organic solvent for toluene, dimethylbenzene, dichloroethanes, dichloromethane, petroleum ether, acetone, butanone, chloroform,
DMF, chloropropane, ethyl acetate.
4. a kind of method for preparing epoxy-modified single second carbide imine class compound according to claim 2, feature exist
Addition reaction temperature is -10-10 DEG C in the step (1).
5. a kind of method for preparing epoxy-modified single second carbide imine class compound according to claim 2, feature exist
Lye includes sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, carbonic acid in the step (1), (2), (3)
Hydrogen potassium.
6. a kind of method for preparing epoxy-modified single second carbide imine class compound according to claim 2, feature exist
Reflux temperature is 40~180 DEG C in the step (2).
7. a kind of method for preparing epoxy-modified single second carbide imine class compound according to claim 2, feature exist
Drier is anhydrous sodium sulfate, anhydrous magnesium sulfate in the step (2).
8. a kind of method for preparing epoxy-modified single second carbide imine class compound according to claim 2, feature exist
In the N, N ' -2,2 ', 6,6 '-tetraalkyl phenyl single second carbide imine and bromine water, bisphenol-A, the molar equivalent of epoxychloropropane
Than being 1:1.05~1.3:1.8-2:1.5-2.
9. a kind of method for preparing epoxy-modified single second carbide imine class compound according to claim 2, feature exist
It is 93% in the yield of the bromo single second carbide imine, the bisphenol-A is 87% for the yield of single second carbide imine, the ring
The yield that oxygen is modified single second carbide imine is 95%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066846A (en) * | 1987-05-29 | 1992-12-09 | 三井石油化学工业株式会社 | A kind of method for preparing epoxy compounds |
| JPH0559031A (en) * | 1991-09-06 | 1993-03-09 | Kagakuhin Kensa Kyokai | Diepoxy compound, its production and its cured product |
| WO2003082218A2 (en) * | 2002-04-03 | 2003-10-09 | Produits Dentaires Pierre Rolland | Photosensitive adhesive composition |
| CN102482242A (en) * | 2009-09-03 | 2012-05-30 | 住友化学株式会社 | Diepoxy compound, process for producing same, and composition containing the diepoxy compound |
| CN103467343A (en) * | 2013-09-16 | 2013-12-25 | 上海朗亿功能材料有限公司 | Novel bi-carbodiimide compound and preparation method thereof |
| CN103556294A (en) * | 2013-10-14 | 2014-02-05 | 江苏恒力化纤股份有限公司 | Creep-resistant hydrolysis-resistance polyester and its preparation method |
-
2016
- 2016-12-20 CN CN201611185814.2A patent/CN108203418B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066846A (en) * | 1987-05-29 | 1992-12-09 | 三井石油化学工业株式会社 | A kind of method for preparing epoxy compounds |
| JPH0559031A (en) * | 1991-09-06 | 1993-03-09 | Kagakuhin Kensa Kyokai | Diepoxy compound, its production and its cured product |
| WO2003082218A2 (en) * | 2002-04-03 | 2003-10-09 | Produits Dentaires Pierre Rolland | Photosensitive adhesive composition |
| CN102482242A (en) * | 2009-09-03 | 2012-05-30 | 住友化学株式会社 | Diepoxy compound, process for producing same, and composition containing the diepoxy compound |
| CN103467343A (en) * | 2013-09-16 | 2013-12-25 | 上海朗亿功能材料有限公司 | Novel bi-carbodiimide compound and preparation method thereof |
| CN103556294A (en) * | 2013-10-14 | 2014-02-05 | 江苏恒力化纤股份有限公司 | Creep-resistant hydrolysis-resistance polyester and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| MATEO ALAJARIN ET AL.: "Domino reactions initiated by intramolecular hydride transfers from tri(di)arylmethane fragments to ketenimine and carbodiimide functions", 《ORG.BIOMOL.CHEM.》 * |
| 庞晓燕 等: "碳化二亚胺型交联剂的合成及性能研究", 《中国皮革》 * |
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