CN111646927A - Derivative of flame-retardant diphenylmethane diisocyanate and synthetic method thereof - Google Patents
Derivative of flame-retardant diphenylmethane diisocyanate and synthetic method thereof Download PDFInfo
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- CN111646927A CN111646927A CN202010535184.7A CN202010535184A CN111646927A CN 111646927 A CN111646927 A CN 111646927A CN 202010535184 A CN202010535184 A CN 202010535184A CN 111646927 A CN111646927 A CN 111646927A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/773—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur halogens
Abstract
The invention relates to a derivative of flame-retardant diphenylmethane diisocyanate and a synthetic method thereof, belonging to the technical field of polyurethane materials. The chemical structural general formula of the derivative of the flame-retardant diphenylmethane diisocyanate is as follows:n(X)NCO‑Ar‑CH2‑Ar‑NCO(X)nwherein Ar is a benzene ring, n is 1-4, and X is Br or Cl; the synthesis method of the derivative of the flame-retardant diphenylmethane diisocyanate comprises the following steps: carrying out condensation reaction on bromoaniline monomer micromolecules and formaldehyde, and sequentially carrying out salification by hydrochloric acid, molecular rearrangement and caustic alkali neutralization reaction to obtain the bromoaniline monomerAnd carrying out phosgenation on the flame-retardant diphenylamine intermediate to obtain the flame-retardant diphenylmethane diisocyanate derivative. The invention has good flame retardant effect, can reduce the addition amount of a physical flame retardant in the polyether polyol component, and realizes the purposes of reducing VOC and odor while realizing high flame retardance.
Description
Technical Field
The invention relates to a derivative of flame-retardant diphenylmethane diisocyanate and a synthetic method thereof, belonging to the technical field of polyurethane materials.
Background
Flame retardancy has always been an important issue facing the polyurethane foam industry. The requirement of fire prevention on the heat insulation material is stricter, the building fire prevention design measures are more and more standardized, the application of polyurethane foam in the fields of building heat insulation and sound insulation is restricted, and particularly, the polyurethane exterior wall heat insulation market continuously slides down since GB 50016-. In the field of passenger cars, the combustion characteristics of the interior decoration materials of GB38262-2019 passenger cars are implemented in 7, month and 1 day of 2020, and the horizontal combustion of a polyurethane seat is specified to be A0 grade, and the vertical combustion is less than or equal to 100 mm/min; the polyurethane thermal insulation noise reduction material needs to have an oxygen index of 25 percent and 28 percent besides horizontal/vertical combustion. In the field of trains: in the seats of high-speed railways and common trains, the oxygen index of the flame retardant property respectively needs to reach 28 percent (the technical condition of flame retardant of the interior material for the motor train unit 2010 of TBT 3237-.
How to improve the flame retardant property of polyurethane foam materials has been a hot spot of research in the industry. Polyurethane foam is formed by the reaction of isocyanate and polyol two components, and research for improving the flame retardance of polyurethane foam plastics is concentrated on the polyol component at present. Mainly through following three kinds of modes:
1. the problems of influencing the physical properties of foam, the migration of a flame retardant and the like exist by adding a phosphorus or halogen liquid flame retardant into a polyol component;
2. the development of the polyhydric alcohol with flame retardant elements such as phosphorus, nitrogen, halogen and the like has the problems of poor physical properties, unsatisfactory flame retardant effect and high cost;
3. the flame retardant is realized by adding solid flame retardants such as expandable graphite, aluminum hydroxide and the like, and the product and process range is narrow.
The existing research on the combination of isocyanate and bromine has the problems of complex process, high cost, low bromine content and the like.
Disclosure of Invention
The invention solves the problem of poor flame retardance of polyurethane foam materials, and provides the derivative of flame-retardant diphenylmethane diisocyanate and the synthesis method thereof, which have good flame-retardant effect, can reduce the addition amount of a physical flame retardant in a polyether polyol component, and realize the purposes of flame retardance and VOC and odor reduction.
The derivative of the flame-retardant diphenylmethane diisocyanate is characterized in that the chemical structural general formula is as follows:n(X)NCO-Ar-CH2-Ar-NCO(X)nwherein Ar is a benzene ring, n is 1-4, and X is Br or Cl;
the chemical structural formula of the derivative of the flame-retardant diphenylmethane diisocyanate is as follows:
the chemical structural formula of the derivative of the flame-retardant diphenylmethane diisocyanate is as follows:
the chemical structural formula of the derivative of the flame-retardant diphenylmethane diisocyanate is as follows:
the synthesis method of the derivative of the flame-retardant diphenylmethane diisocyanate is characterized by comprising the following steps:
the method comprises the following steps of carrying out condensation reaction on bromine-containing aniline monomer micromolecules and formaldehyde, and sequentially carrying out hydrochloric acid salt formation, molecular rearrangement and caustic alkali neutralization reaction to obtain a flame-retardant diphenylamine intermediate, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
the bromoaniline monomer-containing micromolecules are any one of the following chemical structural formulas:
contains single bromine micromolecules, and has the following structural formula:
the structural formula of the double-bromine (chlorine) -containing small molecule is as follows:
the tribromo (chlorine) -containing small molecule has the following structural formula:
the bromine-containing aniline monomer micromolecules are 2-bromoaniline micromolecules, the 2-bromoaniline micromolecules and formaldehyde are subjected to condensation reaction, hydrochloric acid salification, molecular rearrangement and caustic alkali neutralization reaction are sequentially carried out, and the flame-retardant diphenylamine intermediate is obtained, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
the bromine-containing aniline monomer micromolecules are dibromine (chlorine) micromolecules, the dibromine (chlorine) micromolecules and formaldehyde are subjected to condensation reaction, hydrochloric acid salification, molecular rearrangement and caustic alkali neutralization reaction are sequentially carried out, and the flame-retardant diphenylamine intermediate is obtained, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
the bromine-containing aniline monomer micromolecules are tribromo (chlorine) -containing micromolecules, the tribromo (chlorine) -containing micromolecules and formaldehyde are subjected to condensation reaction, hydrochloric acid salt formation, molecular rearrangement and caustic alkali neutralization are sequentially carried out, and a flame-retardant diphenylamine intermediate is obtained through reaction, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
the invention utilizes bromine-containing aniline monomer micromolecules and formaldehyde to carry out condensation reaction, mainly carries out reaction of hydrochloric acid salification, molecular rearrangement, caustic alkali neutralization and the like to obtain a flame-retardant diphenylamine intermediate, and then carries out phosgenation reaction on the flame-retardant diphenylamine intermediate to obtain the derivative of the flame-retardant diphenylmethane diisocyanate. The polyurethane foam material prepared by using the flame-retardant diphenylmethane diisocyanate as a raw material can obtain a higher flame-retardant upper limit on the original flame-retardant level, can also reduce the using amount of an additive flame retardant, reduces the VOC of the material, and provides a new path for improving the flame retardance and the VOC performance of downstream products.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The structural formula of the flame-retardant diphenylmethane diisocyanate derivative of this example is:
the synthesis method of the flame-retardant diphenylmethane diisocyanate derivative of the present embodiment is as follows:
the bromoaniline monomer-containing micromolecular raw material has the following structural formula:
firstly, reacting aniline monomer micromolecules containing bromine with 25-35% of hydrochloric acid catalyst (the molar ratio of the amount of hydrochloric acid to the aniline monomer micromolecules is 0.5-1.0: 1) to generate aniline hydrochloride solution, then dropwise adding 35-39% of formaldehyde water solution (the molar ratio of the amount of formaldehyde to the aniline monomer micromolecules is 0.3-0.5: 1), carrying out condensation reaction for 1-2 h at 80 ℃, then raising the temperature to about 100 ℃, carrying out reaction for 1h, carrying out rearrangement reaction, neutralizing the solution with caustic soda water solution to neutral to obtain flame-retardant diphenylamine intermediate, wherein the reaction equation is as follows:
mixing the flame-retardant diphenylamine intermediate with a dichlorobenzene solvent (0 ℃) (the mass ratio of the flame-retardant diphenylamine intermediate to the dichlorobenzenes is 1: 6-8), introducing dry hydrogen chloride gas to generate diamine hydrochloride slurry (the content is 75%), introducing phosgene (the concentration is 20%), wherein the using amount of the phosgene is 2-5 times (the molar ratio) of the flame-retardant diphenylamine intermediate, reacting at 70 ℃ to form a slurry mixture, heating to 100-200 ℃, reacting for 3-6 hours, and dissolving the slurry to obtain the flame-retardant diphenylmethane diisocyanate derivative. The reaction equation is as follows:
and then carrying out post-treatment procedures such as degassing, high vacuum distillation, purification, separation and the like to obtain the refined flame-retardant diphenyl methane diisocyanate derivative, wherein the Br content of the product is 39.2 percent, and the N content is as follows: 6.9% and an NCO content of 20.6%.
The flame-retardant diphenylmethane diisocyanate derivative of the present example was applied to polyurethane foam:
the formula is as follows:
example 2
The flame-retardant diphenylmethane diisocyanate derivative of the present example has the structural formula:
the synthesis method of the flame-retardant diphenylmethane diisocyanate derivative of the present embodiment is as follows:
the bromoaniline monomer-containing micromolecular raw material has a structural formula shown in the specification;
firstly, reacting aniline monomer micromolecules containing bromine with 25-35% of hydrochloric acid catalyst (the molar ratio of the amount of hydrochloric acid to the aniline monomer micromolecules is 0.5-1.0: 1) to generate aniline hydrochloride solution, then dropwise adding 35-39% of formaldehyde water solution (the molar ratio of the amount of formaldehyde to the aniline monomer micromolecules is 0.3-0.5: 1), carrying out condensation reaction for 1-2 h at 80 ℃, then raising the temperature to about 100 ℃, carrying out reaction for 1h, carrying out rearrangement reaction, neutralizing the solution with caustic soda water solution to neutral to obtain flame-retardant diphenylamine intermediate, wherein the reaction equation is as follows:
mixing the flame-retardant diphenylamine intermediate with a dichlorobenzene solvent (0 ℃) (the mass ratio of the flame-retardant diphenylamine intermediate to the dichlorobenzenes is 1: 6-8), introducing dry hydrogen chloride gas to generate diamine hydrochloride slurry (the content is 75%), introducing phosgene (the concentration is 20%), wherein the using amount of the phosgene is 2-5 times (the molar ratio) of the flame-retardant diphenylamine intermediate, reacting at 70 ℃ to form a slurry mixture, heating to 100-200 ℃, and reacting for 3-6 hours until the slurry is dissolved, thereby obtaining the flame-retardant diisocyanate.
And then carrying out post-treatment procedures such as degassing, high vacuum distillation, purification, separation and the like to obtain the refined flame-retardant diphenyl methane diisocyanate derivative, wherein the Br content of the product is 56.5 percent, and the N content is as follows: 4.9% and an NCO content of 14.8%.
The flame-retardant diphenylmethane diisocyanate derivative of this example was applied to polyurethane foam:
the formula is as follows:
example 3
The flame-retardant diphenylmethane diisocyanate derivative of the present example has the chemical structural formula:
the synthesis method of the flame-retardant diphenylmethane diisocyanate derivative of the embodiment comprises the following steps:
the bromoaniline monomer-containing micromolecular raw material has a chemical structural formula as follows:
firstly, reacting aniline monomer micromolecules containing bromine with 25-35% of hydrochloric acid catalyst (the molar ratio of the amount of hydrochloric acid to the aniline monomer micromolecules is 0.5-1.0: 1) to generate aniline hydrochloride solution, then dropwise adding 35-39% of formaldehyde water solution (the molar ratio of the amount of formaldehyde to the aniline monomer micromolecules is 0.3-0.5: 1), carrying out condensation reaction for 1-2 h at 80 ℃, then raising the temperature to about 100 ℃, carrying out reaction for 1h, carrying out rearrangement reaction, neutralizing the solution with caustic soda water solution to neutral to obtain flame-retardant diphenylamine intermediate, wherein the reaction equation is as follows:
mixing the flame-retardant diphenylamine intermediate with a dichlorobenzene solvent (0 ℃) (the mass ratio of the flame-retardant diphenylamine intermediate to the dichlorobenzenes is 1: 6-8), introducing dry hydrogen chloride gas to generate diamine hydrochloride slurry (the content is 75%), introducing phosgene (the concentration is 20%), wherein the using amount of the phosgene is 2-5 times (the molar ratio) of the flame-retardant diphenylamine intermediate, reacting at 70 ℃ to form a slurry mixture, heating to 100-200 ℃, reacting for 3-6 hours, and dissolving the slurry to obtain the flame-retardant diphenylmethane diisocyanate derivative.
And then carrying out post-treatment procedures such as degassing, high vacuum distillation, purification, separation and the like to obtain the refined flame-retardant diphenyl methane diisocyanate derivative, wherein the Br content of the product is 66.3 percent, and the N content is as follows: 3.9% and NCO content 11.6%.
The flame-retardant diphenylmethane diisocyanate derivative of the present example was applied to polyurethane foam:
the formula is as follows:
example 4
This example uses a polyurethane foam prepared using the conventional polyphenyl methane polyisocyanate product PM200 with no flame retardant properties:
the formula is as follows:
example 5
When the flame-retardant diphenylmethane diisocyanate and the derivative thereof are used to reach the same flame-retardant level as the conventional isocyanate, the comparison of the environmental protection indexes VOC is as follows:
the formula is as follows:
as can be seen from comparison of examples 1 to 4, when the conventional isocyanate PM200 without flame retardant property is used as a raw material, the oxygen index is only 27%, and when the flame retardant diphenylmethane diisocyanate of the present invention is added, the oxygen index can be increased to 30% (example 1), 34% (example 2) and 36% (example 3), and the flame retardant property of the polyurethane foam is greatly improved. In comparison between examples 4 and 5, when the polyurethane foam prepared by using the flame-retardant diphenylmethane diisocyanate as the raw material reaches the same flame-retardant level as that of example 4, the VOC is reduced from 230 mu g to 170 mu g, the VOC is greatly reduced, and the environmental protection performance of the product is improved.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that the present invention may be modified in the foregoing embodiments or equivalents thereof, and for example, the present invention will be modified in detail or substituted in part by the foregoing embodimentsn(X)NCO-Ar-CH2-Ar-NCO(X)nX in (3) can also be F and I elements. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (9)
1. The derivative of flame-retardant diphenylmethane diisocyanate is characterized by having a chemical structural general formula as follows:n(X)NCO-Ar-CH2-Ar-NCO(X)nwherein Ar is a benzene ring, n is 1-4, and X is Br or Cl.
2. The derivative of flame-retardant diphenylmethane diisocyanate according to claim 1, wherein the derivative of flame-retardant diphenylmethane diisocyanate has the chemical formula:
3. the derivative of flame-retardant diphenylmethane diisocyanate according to claim 1, wherein the derivative of flame-retardant diphenylmethane diisocyanate has the chemical formula:
4. the derivative of flame-retardant diphenylmethane diisocyanate according to claim 1, wherein the derivative of flame-retardant diphenylmethane diisocyanate has the chemical formula:
5. a process for the synthesis of the derivatives of flame-retardant diphenylmethane diisocyanates according to any one of claims 1 to 5, comprising the steps of:
the method comprises the following steps of carrying out condensation reaction on bromine-containing aniline monomer micromolecules and formaldehyde, and sequentially carrying out hydrochloric acid salt formation, molecular rearrangement and caustic alkali neutralization reaction to obtain a flame-retardant diphenylamine intermediate, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
6. the method for synthesizing the derivative of flame-retardant diphenylmethane diisocyanate according to claim 5, wherein the bromoaniline monomer small molecule is any one of the following chemical structural formulas:
contains single bromine micromolecules, and has the following structural formula:
the structural formula of the double-bromine (chlorine) -containing small molecule is as follows:
the tribromo (chlorine) -containing small molecule has the following structural formula:
7. the method for synthesizing the derivative of flame-retardant diphenylmethane diisocyanate according to claim 6, wherein the bromoaniline monomer micromolecules are 2-bromoaniline micromolecules, the 2-bromoaniline micromolecules and formaldehyde are subjected to condensation reaction, hydrochloric acid salt formation, molecular rearrangement and caustic alkali neutralization are sequentially carried out, and a flame-retardant diphenylamine intermediate is obtained through reaction, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
8. the method for synthesizing the derivative of flame-retardant diphenylmethane diisocyanate according to claim 6, wherein the bromoaniline monomer micromolecules are dibromine (chlorine) micromolecules, the dibromine (chlorine) micromolecules and formaldehyde are subjected to condensation reaction, hydrochloric acid salt formation, molecular rearrangement and caustic alkali neutralization are sequentially carried out, and a flame-retardant diphenylamine intermediate is obtained through reaction, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
9. the method for synthesizing the derivative of flame-retardant diphenylmethane diisocyanate according to claim 6, wherein the bromoaniline-containing monomer micromolecules are tribromo (chlorine) -containing micromolecules, the tribromo (chlorine) -containing micromolecules are subjected to condensation reaction with formaldehyde, and the flame-retardant diphenylamine intermediate is obtained through salt formation with hydrochloric acid, molecular rearrangement and caustic alkali neutralization reaction in sequence, wherein the reaction equation (1) is as follows:
the flame-retardant diphenylamine intermediate is subjected to phosgenation reaction to obtain the flame-retardant diphenylmethane diisocyanate derivative, and the reaction equation (2) is as follows:
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Cited By (2)
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| CN112480857A (en) * | 2020-11-06 | 2021-03-12 | 南通天洋新材料有限公司 | Flame-retardant moisture-curing polyurethane hot melt adhesive and preparation method thereof |
| WO2022118926A1 (en) * | 2020-12-02 | 2022-06-09 | 東ソー株式会社 | Active hydrogen-containing organic compound scavenger, composition, and applications thereof |
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| CN112480857A (en) * | 2020-11-06 | 2021-03-12 | 南通天洋新材料有限公司 | Flame-retardant moisture-curing polyurethane hot melt adhesive and preparation method thereof |
| WO2022118926A1 (en) * | 2020-12-02 | 2022-06-09 | 東ソー株式会社 | Active hydrogen-containing organic compound scavenger, composition, and applications thereof |
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