CN102731439A - Synthesis method of blocking agent and hydrolysis resistant resin - Google Patents
Synthesis method of blocking agent and hydrolysis resistant resin Download PDFInfo
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- CN102731439A CN102731439A CN2012101875694A CN201210187569A CN102731439A CN 102731439 A CN102731439 A CN 102731439A CN 2012101875694 A CN2012101875694 A CN 2012101875694A CN 201210187569 A CN201210187569 A CN 201210187569A CN 102731439 A CN102731439 A CN 102731439A
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Abstract
The invention discloses synthesis methods of a blocking agent and a hydrolysis resistant resin. The synthesis method of the hydrolysis resistant resin includes the following steps: heating hydrogenated MDI to 150-220 DEG C under anaerobic condition; adding catalyst to conduct a condensation reaction; then adding the blocking agent to conduct a blocking reaction; adding catalyst poisoning agent after stabilization of the reaction system; and discharging after stabilization of the reaction. The finished product obtained by the invention contains two hydrolysis resistant effective structural units of N=C=N structure and epoxy structure, and has good hydrolysis resistant effect; besides, the synthesis route of the invention is simple.
Description
Technical field
The present invention relates to the compound method of a kind of end-capping reagent and anti-hydrolytic resin.
Background technology
Polyester, urethane, gather macromolecular material such as carbon because of containing ester group, carboxamido-group, urea groups isopolarity group, hydrolytic deterioration easily in or the environment that humidity is bigger higher in temperature, thus cause that product performance reduce, the lost of life.The use hydrolysis stabilizer can improve the anti-hydrolytic performance of material, the Application Areas and the work-ing life of widening product.
Organic Carbodiimides can with the compound reaction that contains reactive hydrogen, for example carboxylic acid, alcohol, amine, water etc. therefore can be as the hydrolysis stabilizers of the compound that contains ester group.Because the monomer carbodiimide is owing to the little easy migration loss of molecular weight, and the poly carbodiimide causes indissoluble and infusibility because of forming ring-type or reticulated structure easily, therefore be unfavorable for the processing use.
And common carbodiimide hydrolysis-resisting agent all is the vulcabond that contains phenyl ring, and especially isocyanic ester directly links to each other with phenyl ring.Because when hydrolysis-resisting agent used in adding macromolecule product to, high temperature merged unavoidably.Aromatic hydrocarbon carbodiimide and active hydrogen reaction generate carbamate, at high temperature be cracked into aromatic amine easily, and mostly aromatic amine are toxic compounds.
Summary of the invention
The compound method that the purpose of this invention is to provide a kind of end-capping reagent and anti-hydrolytic resin.
The technical scheme that the present invention taked is:
A kind of compound method of end-capping reagent may further comprise the steps: under the anhydrous and oxygen-free condition, earlier with ethanol and hydrogenation MDI reaction; Temperature of reaction is 100-160 ℃; Reaction times is 0.5-1h, adds glycidyl ether again, continues reaction 2-4h; Wherein, described hydrogenation MDI, glycidyl ether, ethanol mol ratio are 1: (0.2-1): (0.5-2.5).
Described glycidyl ether is a diglycidylether.
A kind of compound method of anti-hydrolytic resin; May further comprise the steps: under anhydrous and oxygen free condition, hydrogenation MDI is warming up to 150-220 ℃, adds catalyzer and carry out polycondensation; Add end-capping reagent again and carry out end capping; After reaction system is stable, adds catalyzer and poison agent, the stable back discharging of reaction system gets final product.
Described oxygen free condition is realized through feeding shielding gas.
The time of polycondensation is 2-8h.
The time of end capping is 0.5-2h.
Described catalyzer is the phospha cyclopentene oxide.
Described catalyst consumption is the 0.1-1.5% of hydrogenation MDI quality.
The mass ratio that described catalyzer and catalyzer poison agent is (1-15): 15.
The invention has the beneficial effects as follows: contain two kinds of anti-hydrolysis resulting structures of N=C=N and epoxy construction unit in the product that the present invention finally obtains, anti-water effect is better, and synthetic route of the present invention is simple.
Description of drawings
The FTIR collection of illustrative plates of the product that Fig. 1 obtains for embodiment 1.
The gpc chromatogram of the product that Fig. 2 obtains for embodiment 2.
The FTIR collection of illustrative plates of the product that Fig. 3 obtains for embodiment 3.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation:
Embodiment 1:
Under logical nitrogen protection and anhydrous condition; Raw material hydrogenation methylenebis phenyl isocyanate 100 gram liter temperature are stirred, and controlled temperature drips 0.1g catalyzer 3-methyl isophthalic acid-phenyl-2-ring fourth phosphorus alkene-1-oxide compound to reaction system and carries out polycondensation at 150 ℃; Polycondensation 8h; Drip oneself interior acyl chlorides of 1.5g then and poison catalyzer, reaction (150 ℃ of temperature of reaction) 1-2h is stable to system again after dropwising is discharging, promptly obtains resin.
Like Fig. 1, through 2119.2cm in the FTIR collection of illustrative plates
-1Place's characteristic peak can find out that carbodiimide groups forms.
Embodiment 2:
Under logical nitrogen protection and anhydrous condition, raw material hydrogenation methylenebis phenyl isocyanate 100 gram liter temperature are stirred, controlled temperature is at 190 ℃; Drip 0.25g catalyzer 3-methyl isophthalic acid-phenyl-2-ring fourth phosphorus alkene-1-oxide compound to reaction system and carry out polycondensation, polycondensation 4h measures the NCO mass contg; Amount of substance according to the isocyanate groups that records; The end-capping reagent of getting equal amount of substance carries out end-blocking, and question response 2h is stable to (190 ℃ of temperature of reaction) system, drips the own interior acyl chlorides of 1.5g then; Reacting 1-2h after dropwising again stable to (190 ℃ of temperature of reaction) system is discharging, promptly obtains anti-hydrolytic resin.
Be illustrated in figure 2 as the MWD collection of illustrative plates of resin.
Embodiment 3:
Under logical nitrogen protection and anhydrous condition, raw material hydrogenation methylenebis phenyl isocyanate 100 gram liter temperature are stirred, controlled temperature is at 220 ℃; Drip 1.5g catalyzer 3-methyl isophthalic acid-phenyl-2-ring fourth phosphorus alkene-1-oxide compound to reaction system and carry out polycondensation, polycondensation 2h measures the NCO mass contg; Amount of substance according to the isocyanate groups that records; The end-capping reagent of getting equal amount of substance carries out end-blocking, and question response 2h is stable to (220 ℃ of temperature of reaction) system, drips oneself interior acyl chlorides of 1.5g then and poisons catalyzer; Dropwise and react 1-2h more stable to be discharging, promptly to obtain anti-hydrolytic resin to (220 ℃ of temperature of reaction) system.
Can see from Fig. 3: 1717 cm
-1Be carbonyl peak, 2120 cm
-1Place's carbodiimide base peak, 3400cm
-1Place's secondary amine base peak, 1030cm
-1The C-O-C of place symmetrical peak.
In the embodiments of the invention, described end-capping reagent is preparation like this: under the anhydrous and oxygen-free condition, earlier with ethanol and hydrogenation MDI reaction; Temperature of reaction is 100-160 ℃, and the reaction times is 0.5-1h, is added dropwise to 1 again; The 4-butanediol diglycidyl ether; Drip and continue reaction 2-4h, wherein, described hydrogenation MDI, glycidyl ether, ethanol mol ratio are 1: (0.2-1): (0.5-2.5).
Claims (9)
1. the compound method of an end-capping reagent is characterized in that: may further comprise the steps: under the anhydrous and oxygen-free condition, earlier with ethanol and hydrogenation MDI reaction; Temperature of reaction is 100-160 ℃; Reaction times is 0.5-1h, adds glycidyl ether again, continues reaction 2-4h; Wherein, described hydrogenation MDI, glycidyl ether, ethanol mol ratio are 1: (0.2-1): (0.5-2.5).
2. the compound method of a kind of end-capping reagent according to claim 1, it is characterized in that: described glycidyl ether is a diglycidylether.
3. the compound method of an anti-hydrolytic resin; It is characterized in that: may further comprise the steps: under anhydrous and oxygen free condition, hydrogenation MDI is warming up to 150-220 ℃, adds catalyzer and carry out polycondensation; Add the described end-capping reagent of claim 1 again and carry out end capping; After reaction system is stable, adds catalyzer and poison agent, the stable back discharging of reaction system gets final product.
4. the compound method of a kind of anti-hydrolytic resin according to claim 1 is characterized in that: described oxygen free condition is realized through feeding shielding gas.
5. the compound method of a kind of anti-hydrolytic resin according to claim 1, it is characterized in that: the time of polycondensation is 2-8h.
6. the compound method of a kind of anti-hydrolytic resin according to claim 1, it is characterized in that: the time of end capping is 0.5-2h.
7. the compound method of a kind of anti-hydrolytic resin according to claim 1, it is characterized in that: described catalyzer is the phospha cyclopentene oxide.
8. the compound method of a kind of anti-hydrolytic resin according to claim 1, it is characterized in that: described catalyst consumption is the 0.1-1.5% of hydrogenation MDI quality.
9. the compound method of a kind of anti-hydrolytic resin according to claim 1 is characterized in that: the mass ratio that described catalyzer and catalyzer poison agent is (1-15): 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210187569.4A CN102731439B (en) | 2012-06-07 | 2012-06-07 | Synthesis method of blocking agent and hydrolysis resistant resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210187569.4A CN102731439B (en) | 2012-06-07 | 2012-06-07 | Synthesis method of blocking agent and hydrolysis resistant resin |
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| CN102731439A true CN102731439A (en) | 2012-10-17 |
| CN102731439B CN102731439B (en) | 2014-12-10 |
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| CN201210187569.4A Active CN102731439B (en) | 2012-06-07 | 2012-06-07 | Synthesis method of blocking agent and hydrolysis resistant resin |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5889096A (en) * | 1996-04-26 | 1999-03-30 | Nisshinbo Industries, Inc. | Hydrolysis stabilizer for ester group-containing resin and process for hydrolysis stabilization of ester group-containing resin using said hydrolysis stabilizer |
| EP0952146A2 (en) * | 1998-04-20 | 1999-10-27 | Nisshinbo Industries, Inc. | Hydrophilic Dicyclohexylmethanecarbodiimide |
-
2012
- 2012-06-07 CN CN201210187569.4A patent/CN102731439B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5889096A (en) * | 1996-04-26 | 1999-03-30 | Nisshinbo Industries, Inc. | Hydrolysis stabilizer for ester group-containing resin and process for hydrolysis stabilization of ester group-containing resin using said hydrolysis stabilizer |
| EP0952146A2 (en) * | 1998-04-20 | 1999-10-27 | Nisshinbo Industries, Inc. | Hydrophilic Dicyclohexylmethanecarbodiimide |
Non-Patent Citations (2)
| Title |
|---|
| 李序霞等: "MDI 基碳化二亚胺耐水解稳定剂的研制", 《聚氨酯工业》 * |
| 谭卓华: "塑料水解稳定剂的研究进展", 《塑料助剂》 * |
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| CN102731439B (en) | 2014-12-10 |
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