WO2015176623A1

WO2015176623A1 - Halogen-free phosphorus-containing flame-retardant rigid polyurethane foam plastic and preparation method therefor

Info

Publication number: WO2015176623A1
Application number: PCT/CN2015/079037
Authority: WO
Inventors: 戴李宗; 谢聪; 袁丛辉; 毛杰; 刘诚; 陈国荣; 许一婷; 罗伟昂; 曾碧榕; 常迎
Original assignee: 厦门大学
Priority date: 2014-05-21
Filing date: 2015-05-15
Publication date: 2015-11-26
Also published as: CN103965432A; CN103965432B

Abstract

A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam plastic and a preparation method therefor. The halogen-free phosphorus-containing flame-retardant rigid polyurethane foam plastic comprises a phosphorus-containing reactive flame retardant 9,10-dihydro-9-oxa-10-phospha-10-oxidized phenanthryl terephthalyl alcohol, the chemical structural formula thereof being (I). A series of flame-retardant rigid polyurethane foam plastics with different phosphorus contents can be prepared by changing the dosages of a flame retardant and a polyether polyol. The phosphorus-containing foam plastics can generate a phosphorus-rich coke layer with a better heat stability when decomposed, and the phosphorus-rich coke layer can inhibit the continuous combustion of the matrix resin and can also effectively inhibit the generation of a combustible gas.

Description

Halogen-free phosphorus-containing flame-retardant rigid polyurethane foam and preparation method thereof

Technical field

The invention belongs to the technical field of materials, and in particular relates to a halogen-free phosphorus-containing flame-retardant rigid polyurethane foam and a preparation method thereof.

Background technique

As a polymer material, polyurethane is widely used in bonding, coating and other industries. However, the lack of flame retardant performance has become one of the bottleneck factors restricting the application of polyurethane. For example, in the field of civil engineering, transportation, such as automobiles and aircrafts, due to the harsh conditions of use, more stringent requirements are imposed on the flame retardant properties of polyurethane. Polyurethane flame retardant modification is mainly concentrated on additive flame retardant technology. Chinese patent CN1639245 discloses a flame-retardant thermoplastic polyurethane composition containing melamine cyanurate as the sole organic flame retardant additive, which has excellent physical properties, and has low LOI% and low peak heat release. rate. Chinese patent CN101161922 separates a flame-retardant polyurethane synthetic leather and a preparation method thereof, and the raw material component of the flame-retardant polyurethane synthetic leather comprises a nitrogen-phosphorus composite flame retardant, a solvent-based polyurethane, and the nitrogen-phosphorus composite flame retardant The raw material component of the dispersion system is formulated as follows: 0.5-2.0 parts of phosphorus titanate and 60-110 parts of solvent. The nitrogen-phosphorus composite flame retardant is mainly phosphorus, supplemented by nitrogen, phosphorus and nitrogen. The flame retardant polyurethane synthetic leather has high efficiency flame retardancy at a ratio of 4:1 to 2:1. The use of traditional additive flame retardants has been unable to meet the requirements of high efficiency flame retardant, environmentally friendly, and good compatibility with the substrate. At the same time, traditional halogen flame retardants have been subject to increasingly stringent environmental and flame retardant laws and regulations, forcing researchers to seek alternatives to halogen flame retardants.

Summary of the invention

It is an object of the present invention to provide a halogen-free phosphorus-containing flame retardant rigid polyurethane foam.

Another object of the present invention is to provide a halogen-free phosphorus-containing flame-retardant rigid polyurethane foam. Preparation.

The technical solution of the present invention is as follows:

A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam comprising a phosphorus-containing reactive flame retardant, the name of the phosphorus-containing reactive flame retardant is 9,10-dihydro-9-oxa-10-phosphorus ‐10‐ phenoxy-p-phenylene dimethanol (DOPO‐t‐DM), whose chemical structural formula is:

The preparation method can be referred to the literature: Liu, Ying Ling; Wu, Chuan Shao; Hsu, Keh Ying; Chang, Teh Chou. Flame-retardant epoxy resins from o-cresol novolac epoxy cured with a phosphorus-containing aralkyl novolac [J]. Journal of Polymer Science, Part A: Polymer Chemistry (2002), 40(14), 2329‐2339.

In a preferred embodiment of the invention, the following components by weight are included:

The phosphorus-containing reactive flame retardant accounts for 10% to 90% of the total mass of the polyether polyol and the phosphorus-containing reactive flame retardant to adjust the phosphorus content.

In a preferred embodiment of the invention, the polyether polyol has an average functionality of from 4.7 to 5.0 and a hydroxyl number of from 430 to 470 mg KOH/g. (Also can be used for any other commercial polyurethane)

In a preferred embodiment of the present invention, the polymethylene polyphenyl isocyanate has a viscosity of 150 to 250 mPa·s and a mass percentage of the isocyanate functional group of 30.2% to 32.0%.

In a preferred embodiment of the invention, the tertiary amine catalyst is a dipropylene glycol solution of ethylene diamine in a mass percent concentration of 33%, abbreviated as A-33.

In a preferred embodiment of the invention, the 2,4,6-tris(dimethylaminomethyl)phenol has an amine number of from 600 to 630 mg KOH/g and a moisture content of less than 0.01%.

In a preferred embodiment of the invention, the blowing agent may be water and/or cyclopentane in an amount of 50% by weight based on the total mass of the cyclopentane.

Another technical solution of the present invention is as follows:

A preparation method of the above halogen-free phosphorus-containing flame-retardant rigid polyurethane foam comprises the following steps:

(1) The phosphorus-containing reactive flame retardant, polyether polyol, tertiary amine catalyst, dibutyltin dilaurate, silicon carbon bond type foam stabilizer, 2,4,6-tris (dimethylaminol) Base) phenol and foaming agent are mixed evenly to obtain a mixture;

(2) The polymethylene polyphenyl isocyanate is added to the above mixture, poured into a mold, and sequentially foamed and aged, and the rigid polyurethane foam is obtained after demolding.

The beneficial effects of the invention are:

(1) The phosphorus-containing reactive flame retardant of the present invention, like the polyether polyol, is a difunctional alcohol which functions as a polyether polyol and also contains a flame retardant element phosphorus;

(2) The plastic of the present invention can prepare a series of flame-retardant rigid polyurethane foams with different phosphorus contents by changing the amount of the flame retardant and the polyether polyol, and the phosphorus-containing foams can be thermally stable when decomposed. A preferred phosphorus-rich coke layer which inhibits the continued combustion of the matrix resin and also effectively suppresses the generation of combustible gases.

(3) The rigid polyurethane foam of the present invention directly uses a reactive flame retardant technique to introduce a phosphorus-containing compound into a polyurethane molecule in the form of a covalent bond, thereby overcoming the poor compatibility of the conventional additive flame retardant with the matrix, and after a long period of time The disadvantage of easy migration, at the same time, compared with the added flame retardant, the situation of reducing the amount is greatly improved. Its flame retardant efficiency.

detailed description

The technical solutions of the present invention are further illustrated and described below by way of specific embodiments.

Example 1

Weigh 100g of polyether polyol 4110, 1.2g of tertiary amine catalyst and 0.03g of dibutyltin dilaurate, 1.2g of silicon carbon bond type foam stabilizer, 1.2g of 2,4,6-tris(dimethylaminomethyl) Phenol, 0.2 g of water and 0.4 g of cyclopentane were uniformly mixed under high speed stirring. 120 g of polymethylene polyphenyl isocyanate was quickly added, and the mixture was uniformly stirred at a high temperature of 2500 r/min at room temperature. When the mixture was observed to be whitish, it was poured into a self-made mold and freely foamed. After foaming, it was aged for 48 hours, and the mold was released to obtain a rigid polyurethane foam. Its oxygen index is 17.0 (GB/T 2406.1-2008).

Example 2

Weigh 90g of polyether polyol 4110, 10g of phosphorus-containing reactive flame retardant of the invention, 2.2g of tertiary amine catalyst and 0.07g of dibutyltin dilaurate, 2.2g of silicon carbon bond type foam stabilizer, 2.2g 2, 4,6-Tris(dimethylaminomethyl)phenol, 0.2 g of water and 0.4 g of cyclopentane were uniformly mixed under high speed stirring. 120 g of polymethylene polyphenyl isocyanate was quickly added, and the mixture was uniformly stirred at a high temperature of 2500 r/min at room temperature. When the mixture was observed to be whitish, it was poured into a self-made mold and freely foamed. After foaming, it was aged for 48 hours, and the mold was released to obtain a rigid polyurethane foam. Its oxygen index is 19.0 (GB/T 2406.1-2008).

Example 3

Weigh 80g of polyether polyol 4110, 20g of phosphorus-containing reactive flame retardant of the invention, 1.5g of tertiary amine catalyst and 0.05g of dibutyltin dilaurate, 1.5g of silicon carbon bond type foam stabilizer, 1.5g 2, 4,6-Tris(dimethylaminomethyl)phenol, 0.2 g of water and 0.4 g of cyclopentane were uniformly mixed under high speed stirring. 120 g of polymethylene polyphenyl isocyanate was quickly added, and the mixture was uniformly stirred at a high temperature of 2500 r/min at room temperature. When the mixture was observed to be whitish, it was poured into a self-made mold and freely foamed. After foaming, it was aged for 48 hours, and the mold was released to obtain a rigid polyurethane foam. Its oxygen index is 21.0 (GB/T 2406.1-2008).

Examples 4 to 10

The rigid polyurethane foam of these examples was prepared in the same manner as in Example 1. By changing the ratio of the polyether polyol 4110 and the phosphorus-containing reactive flame retardant of the present invention, a series of flame retardant polyurethanes having different phosphorus contents are prepared, as shown in Table 1 below:

Table 1

The above is only the preferred embodiment of the present invention, and thus the scope of the present invention is not limited thereto, and equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the specification should still be covered by the present invention. In the range.

Industrial applicability

The phosphorus-containing reactive flame retardant of the present invention is a difunctional alcohol which functions as a polyether polyol and also contains a flame retardant element phosphorus.

Claims

A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam characterized by comprising a phosphorus-containing reactive flame retardant whose name is 9,10-dihydro-9-oxo- 10‐phosphonium-10-oxophenanthrene-p-phenylenediethanol, its chemical structural formula is:
A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to claim 1, which comprises the following components by weight:
A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to claim 2, wherein said phosphorus-containing reactive flame retardant comprises total mass of polyether polyol and said phosphorus-containing reactive flame retardant 10% to 90% to adjust the phosphorus content.
A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to claim 2, wherein said polyether polyol has an average functionality of from 4.7 to 5.0 and a hydroxyl value of from 430 to 470 mgKOH/g.
A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to claim 2, wherein said polymethylene polyphenyl isocyanate has a viscosity of 150 to 250 mPa·s and an isocyanate functional group. The mass percentage content is from 30.2% to 32.0%.
A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to claim 2, wherein the tertiary amine catalyst is a dipropylene glycol solution of ethylene diamine in a mass percentage of 33%.
A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to claim 2, wherein said 2,4,6-tris(dimethylaminomethyl)phenol has an amine value of 600 to 630 mgKOH /g, moisture is less than 0.01%.
A halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to claim 2, wherein said blowing agent is water and/or cyclopentane.
A method for preparing a halogen-free phosphorus-containing flame-retardant rigid polyurethane foam according to any one of claims 2 to 8, characterized in that it comprises the following steps:

(1) The phosphorus-containing reactive flame retardant, polyether polyol, tertiary amine catalyst, dibutyltin dilaurate, silicon carbon bond type foam stabilizer, 2,4,6-tris (dimethylaminol) Base) phenol and foaming agent are mixed evenly to obtain a mixture;

(2) The polymethylene polyphenyl isocyanate is added to the above mixture, poured into a mold, and sequentially foamed and aged, and the rigid polyurethane foam is obtained after demolding.