CN112794987A - Flame-retardant polyurea-polyurethane - Google Patents
Flame-retardant polyurea-polyurethane Download PDFInfo
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
Abstract
The invention belongs to the field of new materials. The invention relates to flame-retardant polyurea-polyurethane, which is prepared from allyl amine, DOPO, 3-chloropropyltrimethoxysilane, dihydroxy-terminated polysiloxane and TDI as raw materials through multi-step reactions such as addition, substitution, amidation and the like. The novel flame-retardant polyurea-polyurethane not only effectively overcomes the defects that the conventional high-molecular organic material is inflammable and the flame-retardant effect of the conventional flame retardant is poor, but also can be used as a flame-retardant raw material or a high-efficiency flame retardant, and has better hydrophobic property, and the material is particularly suitable for the fields of building materials, industrial materials and the like.
Description
Technical Field
The invention relates to a flame-retardant polyurea-polyurethane. The invention belongs to the field of new materials.
Background
As is well known, the popularization of organic polymer materials greatly facilitates the life of people. The polymer material is an indispensable existence in life, but most of the polymer materials are inflammable materials. For example, chemical fiber and cotton fiber are used as one of the most commonly used textile raw materials, the limited oxygen index is only 18%, and the chemical fiber and the cotton fiber are extremely easy to burn, so that fire hazards are caused to the safety of human life and property. Therefore, it must be subjected to flame retardant finishing to improve its fire resistance. The most common means is to add flame retardant with flame retardant function into polymer system, however, the conventional flame retardant is toxic or releases toxic gas and smoke in the combustion process, and a large amount of flame retardant is needed to achieve the flame retardant level.
With the development of social economy, health and environmental protection problems become hot points of people's attention increasingly, the green development strategy becomes more an important development strategy of the country, and the intumescent nitrogen-phosphorus flame retardant meets the environmental protection requirement of protecting the ecological environment in the current era due to the unique flame retardant mechanism and the characteristics of low smoke, no toxicity, molten drop resistance and the like, and is the development trend of flame retardant materials in future. Among them, 9, 10-dihydro-9-oxa-10-phenanthrene-10-oxide (DOPO) and its derivatives have biphenyl, phenanthrene ring, O ═ P-O structure in the structure, so that it has the advantages of migration resistance and good flame-retardant property, and can be entered into the field of scientific research personnel, and at present, many new flame retardants are developed on the basis of DOPO.
In view of the flammable characteristics of most of the current high polymer materials and the problems of environmental protection, safety and low flame retardant efficiency of the flame retardant, it is important to develop a flame retardant with high-efficiency flame retardant effect and even a flame-retardant raw material.
Disclosure of Invention
The invention aims to solve the problems that high molecular organic materials are flammable and the flame retardant effect of the existing flame retardant is poor in the prior art, and provides flame-retardant polyurea-polyurethane, which is prepared from allyl amine, DOPO, 3-chloropropyltrimethoxysilane, dihydroxy-terminated polysiloxane and TDI through multi-step reactions such as addition, substitution, amidation and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a flame retardant polyurea-polyurethane having the structural formula:
wherein n is 5 to 11.
A method of preparing a flame retardant polyurea-polyurethane comprising the steps of:
(1) dissolving 1mol of DOPO and 1-1.2mol of allyl amine in 50mol of 1, 4-dioxane, adding into a flask, adding 1-2 wt% of AIBN, placing into the flask, carrying out oil bath at 70-80 ℃ for 8-12h, after the reaction is finished, carrying out reduced pressure distillation, dissolving into dichloromethane, respectively washing for 3 times with 1M sodium hydroxide aqueous solution and deionized water until the solution is neutral, separating the solution, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain an intermediate product I;
the AIBN dosage is the mass percentage of DOPO;
(2) adding 1mol of I, 1.2-1.5mol of 3-chloropropyltrimethoxysilane and 4mol of triethylamine into a flask containing 30mol of dichloromethane, stirring at room temperature for 12-18h, adding 40mol of deionized water into the mixture after the reaction is finished, separating liquid, taking an organic phase, distilling under reduced pressure, and drying in vacuum to obtain an intermediate product II;
(3) adding 1mol of II and 0.4-0.5mol of dihydroxy polysiloxane into a flask filled with 50mol of methanol, mixing, stirring, cooling to 0 ℃, adding 0.01mol of strontium hydroxide into the flask, keeping the temperature at 0 ℃ for reaction for 8-12h, filtering to remove the strontium hydroxide after the reaction is finished, adding 5-6 wt% of cation exchange resin, oscillating for 30min, filtering, removing the solvent under reduced pressure, and vacuum drying to obtain an intermediate product III;
the dosage of the cation exchange resin is the mass percent of the dihydroxy polysiloxane;
(4) placing 2mol of TDI in a flask, heating to 70-90 ℃, introducing protective gas, dissolving 1mol of III in 50mol of anhydrous organic solvent, placing in a constant pressure dropping funnel, slowly dropping into the flask, and continuously stirring for 12-24h after dropping is finished to obtain a target product IV.
Preferably, the polymerization degree n of the bishydroxypolysiloxane is 5 to 11.
Preferably, the cation exchange resin is WK-40, D113 or IRC-84.
Preferably, the protective gas is nitrogen or argon.
Preferably, the anhydrous organic solvent is cyclohexanone, DMF, 1, 4-dioxane or toluene.
The preparation process of the novel flame-retardant polyurea-polyurethane provided by the invention comprises the following steps:
the invention has the beneficial effects that:
(1) the invention provides flame-retardant polyurea-polyurethane, the molecular structure of which contains bimolecular reaction type flame retardant DOPO, the polyurea-polyurethane structure of which contains high N content, can form a polycyclic structure of a stable carbonization layer, a high-temperature resistant siloxane structure and the like, and is a novel expansion type nitrogen-phosphorus flame retardant integrating an acid source, a carbon source and a gas source.
(2) The invention provides flame-retardant polyurea-polyurethane, wherein an active isocyanate structural group exists in a molecular structure, so that the flame-retardant polyurea-polyurethane can be used as a reactive flame retardant.
(3) The invention provides flame-retardant polyurea-polyurethane, wherein a target product contains a plurality of active isocyanate structural groups, high-temperature-resistant rigid benzene rings and high-temperature-resistant flexible siloxane structures, and can be directly used as a flame-retardant polyurea-polyurethane material.
(4) The invention provides flame-retardant polyurea-polyurethane, which has a wide application prospect in the fields of building materials and interior decoration materials.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Example 1
A method of preparing a flame retardant polyurea-polyurethane comprising the steps of:
(1) dissolving 1mol of DOPO and 1.2mol of allyl amine in 50mol of 1, 4-dioxane, adding the mixture into a flask, adding 1 wt% of AIBN, placing the mixture into the flask, carrying out oil bath at 75 ℃ for 10 hours, carrying out reduced pressure distillation after the reaction is finished, dissolving the mixture into dichloromethane, washing the mixture for 3 times respectively with 1M sodium hydroxide aqueous solution and deionized water until the mixture is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain an intermediate product I;
the AIBN dosage is the mass percentage of DOPO;
the infrared data are as follows: 3342cm-1：-NH2A spike is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1611cm-1: -C ═ C — disappearance.
(2) Adding 1mol of I, 1.5mol of 3-chloropropyltrimethoxysilane and 4mol of triethylamine into a flask containing 30mol of dichloromethane, stirring for 12 hours at room temperature, adding 40mol of deionized water into the mixture after the reaction is finished, separating liquid, taking an organic phase, distilling under reduced pressure, and drying in vacuum to obtain an intermediate product II;
the infrared data are as follows: 3342cm-1：-NH2The peak disappears; 3121cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 1150cm-1: -Si-O-is present; 706cm-1: disappearance of-C-Cl.
(3) Adding 1mol of II and 0.5mol of dihydroxypolysiloxane (n is 5) into a flask containing 50mol of methanol, mixing, stirring, cooling to 0 ℃, adding 0.01mol of strontium hydroxide into the flask, keeping the temperature at 0 ℃ for reaction for 12h, filtering to remove the strontium hydroxide after the reaction is finished, adding 5 wt% of cation exchange resin WK-40, oscillating for 30min, filtering, removing the solvent under reduced pressure, and drying in vacuum to obtain an intermediate product III;
the dosage of the cation exchange resin is the mass percent of the dihydroxy polysiloxane;
the infrared data are as follows: 3121cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 3527cm-1: -OH disappears.
(4) Placing 2mol of TDI in a flask, heating to 80 ℃, introducing nitrogen, dissolving 1mol of III in 50mol of anhydrous cyclohexanone, placing in a constant pressure dropping funnel, slowly dropping into the flask, and continuously stirring for 15h after dropping is finished to obtain a target product IV.
The infrared data are as follows: 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 1650cm-1、1520cm-1: the presence of an amide; 2270cm-1: -NCO is present.
The nuclear magnetic hydrogen spectrum data is as follows:1h NMR (400MHz, DMSO,. delta.ppm): 7.0-7.9(22H, benzene ring); 2.53(4H, -CH)2-)；1.26(12H，-CH2-)；3.13(8H，-CH2-)；8.37(2H，-NH-)；2.71(6H，-CH3)；3.39(12H，-CH3)；0.84(36H，-CH3)。
Example 2
A method of preparing a flame retardant polyurea-polyurethane comprising the steps of:
(1) dissolving 1mol of DOPO and 1mol of allyl amine in 50mol of 1, 4-dioxane, adding the mixture into a flask, adding 2 wt% of AIBN, placing the mixture into the flask, carrying out oil bath at 70 ℃ for 12 hours, carrying out reduced pressure distillation after the reaction is finished, dissolving the mixture into dichloromethane, washing the mixture for 3 times to be neutral respectively by using 1M of sodium hydroxide aqueous solution and deionized water, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain an intermediate product I;
the AIBN dosage is the mass percentage of DOPO;
the infrared data are as follows: 3343cm-1：-NH2A spike is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1191cm-1: P-O-is present; 1611cm-1: -C ═ C — disappearance.
(2) Adding 1mol of I, 1.4mol of 3-chloropropyltrimethoxysilane and 4mol of triethylamine into a flask containing 30mol of dichloromethane, stirring for 15h at room temperature, adding 40mol of deionized water into the mixture after the reaction is finished, separating liquid, taking an organic phase, distilling under reduced pressure, and drying in vacuum to obtain an intermediate product II;
the infrared data are as follows: 3343cm-1：-NH2The peak disappears; 3122cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1191cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 1150cm-1: -Si-O-is present; 706cm-1: disappearance of-C-Cl.
(3) Adding 1mol of II and 0.4mol of dihydroxypolysiloxane (n is 7) into a flask containing 50mol of methanol, mixing, stirring, cooling to 0 ℃, adding 0.01mol of strontium hydroxide into the flask, keeping the temperature at 0 ℃ for reaction for 8h, filtering to remove the strontium hydroxide after the reaction is finished, adding 6 wt% of cation exchange resin D113, oscillating for 30min, filtering, removing the solvent under reduced pressure, and drying in vacuum to obtain an intermediate product III;
the dosage of the cation exchange resin is the mass percent of the dihydroxy polysiloxane;
the infrared data are as follows: 3122cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1191cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 3527cm-1: -OH disappears.
(4) Placing 2mol of TDI in a flask, heating to 90 ℃, introducing argon, dissolving 1mol of III in 50mol of anhydrous DMF, placing in a constant pressure dropping funnel, slowly dropping into the flask, and continuously stirring for 12h after dropping is finished to obtain a target product IV.
The infrared data are as follows: 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1191cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 1650cm-1、1520cm-1: the presence of an amide; 2270cm-1: -NCO is present.
The nuclear magnetic hydrogen spectrum data is as follows:1h NMR (400MHz, DMSO,. delta.ppm): 7.0-7.9(22H, benzene ring); 2.53(4H, -CH)2-)；1.26(12H，-CH2-)；3.13(8H，-CH2-)；8.37(2H，-NH-)；2.71(6H，-CH3)；3.39(12H，-CH3)；0.84(36H，-CH3)。
Example 3
A method of preparing a flame retardant polyurea-polyurethane comprising the steps of:
(1) dissolving 1mol of DOPO and 1.1mol of allyl amine in 50mol of 1, 4-dioxane, adding the mixture into a flask, adding 1 wt% of AIBN, placing the mixture into the flask, carrying out oil bath at 80 ℃ for 8 hours, carrying out reduced pressure distillation after the reaction is finished, dissolving the mixture into dichloromethane, washing the mixture for 3 times respectively with 1M sodium hydroxide aqueous solution and deionized water until the mixture is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain an intermediate product I;
the AIBN dosage is the mass percentage of DOPO;
the infrared data are as follows: 3347cm-1：-NH2A spike is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1304cm-1: p ═ O present; 1195cm-1: P-O-is present; 1611cm-1: -C ═ C — disappearance.
(2) Adding 1mol of I, 1.2mol of 3-chloropropyltrimethoxysilane and 4mol of triethylamine into a flask containing 30mol of dichloromethane, stirring for 18h at room temperature, adding 40mol of deionized water into the mixture after the reaction is finished, separating liquid, taking an organic phase, distilling under reduced pressure, and drying in vacuum to obtain an intermediate product II;
the infrared data are as follows: 3347cm-1：-NH2The peak disappears; 3125cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1304cm-1: p ═ O present; 1195cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 1149cm-1: -Si-O-is present; 706cm-1: disappearance of-C-Cl.
(3) Adding 1mol of II and 0.4mol of dihydroxypolysiloxane (n is 11) into a flask containing 50mol of methanol, mixing, stirring, cooling to 0 ℃, adding 0.01mol of strontium hydroxide into the flask, keeping the temperature at 0 ℃ for reaction for 10 hours, filtering to remove the strontium hydroxide after the reaction is finished, adding 6 wt% of cation exchange resin IRC-84, oscillating for 30min, filtering, removing the solvent under reduced pressure, and drying in vacuum to obtain an intermediate product III;
the dosage of the cation exchange resin is the mass percent of the dihydroxy polysiloxane;
the infrared data are as follows: 3125cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1304cm-1: p ═ O present; 1195cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 3527cm-1: -OH disappears.
(4) Placing 2mol of TDI in a flask, heating to 70 ℃, introducing nitrogen, dissolving 1mol of III in 50mol of anhydrous toluene, placing in a constant pressure dropping funnel, slowly dropping into the flask, and continuing stirring for 24h after dropping is finished to obtain a target product IV.
The infrared data are as follows: 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1304cm-1: p ═ O present; 1195cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: presence of-Si-O-Si-；1651cm-1、1523cm-1: the presence of an amide; 2270cm-1: -NCO is present.
The nuclear magnetic hydrogen spectrum data is as follows:1h NMR (400MHz, DMSO,. delta.ppm): 7.0-7.9(22H, benzene ring); 2.53(4H, -CH)2-)；1.26(12H，-CH2-)；3.13(8H，-CH2-)；8.37(2H，-NH-)；2.71(6H，-CH3)；3.39(12H，-CH3)；0.84(36H，-CH3)。
Example 4
A method of preparing a flame retardant polyurea-polyurethane comprising the steps of:
(1) dissolving 1mol of DOPO and 1.2mol of allyl amine in 50mol of 1, 4-dioxane, adding the mixture into a flask, adding 1.5 wt% of AIBN, placing the mixture into the flask, carrying out oil bath at 75 ℃ for 8 hours, carrying out reduced pressure distillation after the reaction is finished, dissolving the mixture into dichloromethane, washing the mixture for 3 times respectively with 1M sodium hydroxide aqueous solution and deionized water until the mixture is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain an intermediate product I;
the AIBN dosage is the mass percentage of DOPO;
the infrared data are as follows: 3342cm-1：-NH2A spike is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1611cm-1: -C ═ C — disappearance.
(2) Adding 1mol of I, 1.5mol of 3-chloropropyltrimethoxysilane and 4mol of triethylamine into a flask containing 30mol of dichloromethane, stirring for 14h at room temperature, adding 40mol of deionized water into the mixture after the reaction is finished, separating liquid, taking an organic phase, distilling under reduced pressure, and drying in vacuum to obtain an intermediate product II;
the infrared data are as follows: 3342cm-1：-NH2The peak disappears; 3121cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present;1258cm-1、798cm-1: -Si-C-is present; 1145cm-1: -Si-O-is present; 706cm-1: disappearance of-C-Cl.
(3) Adding 1mol of II and 0.5mol of dihydroxypolysiloxane (n is 9) into a flask containing 50mol of methanol, mixing, stirring, cooling to 0 ℃, adding 0.01mol of strontium hydroxide into the flask, keeping the temperature at 0 ℃ for reaction for 10 hours, filtering to remove the strontium hydroxide after the reaction is finished, adding 5 wt% of cation exchange resin WK-40, oscillating for 30min, filtering, removing the solvent under reduced pressure, and drying in vacuum to obtain an intermediate product III;
the dosage of the cation exchange resin is the mass percent of the dihydroxy polysiloxane;
the infrared data are as follows: 3121cm-1: -NH-is present; 3066cm-1: a benzene ring-C-H exists; 2922cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 3527cm-1: -OH disappears.
(4) Placing 2mol of TDI in a flask, heating to 80 ℃, introducing argon, dissolving 1mol of III in 50mol of anhydrous 1, 4-dioxane, placing in a constant pressure dropping funnel, slowly dropping into the flask, and continuing stirring for 18h after dropping is finished to obtain a target product IV.
The infrared data are as follows: 3066cm-1: a benzene ring-C-H exists; 2922cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 1650cm-1、1520cm-1: the presence of an amide; 2271cm-1: -NCO is present.
The nuclear magnetic hydrogen spectrum data is as follows:1h NMR (400MHz, DMSO,. delta.ppm): 7.0-7.9(22H, benzene ring); 2.53(4H, -CH)2-)；1.26(12H，-CH2-)；3.13(8H，-CH2-)；8.37(2H，-NH-)；2.71(6H，-CH3)；3.39(12H，-CH3)；0.84(36H，-CH3)。
Example 5
A method of preparing a flame retardant polyurea-polyurethane comprising the steps of:
(1) dissolving 1mol of DOPO and 1.1mol of allyl amine in 50mol of 1, 4-dioxane, adding the mixture into a flask, adding 2 wt% of AIBN, placing the mixture into the flask, carrying out oil bath at 80 ℃ for 8 hours, carrying out reduced pressure distillation after the reaction is finished, dissolving the mixture into dichloromethane, washing the mixture for 3 times respectively with 1M sodium hydroxide aqueous solution and deionized water until the mixture is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain an intermediate product I;
the AIBN dosage is the mass percentage of DOPO;
the infrared data are as follows: 3343cm-1：-NH2A spike is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1611cm-1: -C ═ C — disappearance.
(2) Adding 1mol of I, 1.5mol of 3-chloropropyltrimethoxysilane and 4mol of triethylamine into a flask containing 30mol of dichloromethane, stirring for 15h at room temperature, adding 40mol of deionized water into the mixture after the reaction is finished, separating liquid, taking an organic phase, distilling under reduced pressure, and drying in vacuum to obtain an intermediate product II;
the infrared data are as follows: 3343cm-1：-NH2The peak disappears; 3121cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 1150cm-1: -Si-O-is present; 706cm-1: disappearance of-C-Cl.
(3) Adding 1mol of II and 0.4mol of dihydroxypolysiloxane (n is 5) into a flask containing 50mol of methanol, mixing, stirring, cooling to 0 ℃, adding 0.01mol of strontium hydroxide into the flask, keeping the temperature at 0 ℃ for reaction for 10 hours, filtering to remove the strontium hydroxide after the reaction is finished, adding 6 wt% of cation exchange resin WK-40, oscillating for 30min, filtering, removing the solvent under reduced pressure, and drying in vacuum to obtain an intermediate product III;
the dosage of the cation exchange resin is the mass percent of the dihydroxy polysiloxane;
the infrared data are as follows: 3121cm-1: -NH-is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 3527cm-1: -OH disappears.
(4) Placing 2mol of TDI in a flask, heating to 80 ℃, introducing nitrogen, dissolving 1mol of III in 50mol of anhydrous toluene, placing in a constant pressure dropping funnel, slowly dropping into the flask, and continuously stirring for 20h after dropping is finished to obtain a target product IV.
The infrared data are as follows: 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present; 1258cm-1、798cm-1: -Si-C-is present; 970-1150cm-1: -Si-O-Si-is present; 1650cm-1、1520cm-1: the presence of an amide; 2270cm-1: -NCO is present.
The nuclear magnetic hydrogen spectrum data is as follows:1h NMR (400MHz, DMSO,. delta.ppm): 7.0-7.9(22H, benzene ring); 2.53(4H, -CH)2-)；1.26(12H，-CH2-)；3.13(8H，-CH2-)；8.37(2H，-NH-)；2.71(6H，-CH3)；3.39(12H，-CH3)；0.84(36H，-CH3)。
The novel flame-retardant polyurea-polyurethane obtained in the specific example 1 is used as a base material of an application example, and is made into a flame-retardant material. Wherein the NCO content is 12.5% in comparison with TDI in the target product IV.
Application example 1
A flame-retardant coating comprises the following raw materials in parts by weight:
330100 parts of polyether, 32 parts of TDI, 21 parts of a target product IV, 0.2 part of stannous octoate, 0.1 part of triethylene diamine, 0.3 part of tourmaline powder and 30 parts of DMF.
Application example 2
A flame-retardant coating comprises the following raw materials in parts by weight:
330100 parts of polyether, 32 parts of TDI, 28 parts of a target product IV, 0.2 part of stannous octoate, 0.1 part of triethylene diamine, 0.3 part of tourmaline powder and 30 parts of DMF.
Application example 3
A flame-retardant coating comprises the following raw materials in parts by weight:
330100 parts of polyether, 33 parts of TDI, 14 parts of a target product IV, 0.2 part of stannous octoate, 0.1 part of triethylene diamine, 0.3 part of tourmaline powder and 30 parts of DMF.
Application example 4
A flame-retardant coating comprises the following raw materials in parts by weight:
330100 parts of polyether, 280 parts of target product IV, 0.2 part of stannous octoate, 0.1 part of triethylene diamine, 0.3 part of tourmaline powder and 30 parts of DMF.
The flame retardant coatings of comparative examples 1 to 5 were applied in comparison with the flame retardant coating of application example 1:
practical example comparative example 1
A flame-retardant coating comprises the following raw materials in parts by weight:
330100 parts of polyether, 32 parts of TDI, 0.2 part of stannous octoate, 0.1 part of triethylene diamine, 0.3 part of tourmaline powder and 30 parts of DMF.
Practical example comparative example 2
A flame-retardant coating comprises the following raw materials in parts by weight:
330100 parts of polyether, 32 parts of TDI, 21 parts of DOPO, 0.2 part of stannous octoate, 0.1 part of triethylene diamine, 0.3 part of tourmaline powder and 30 parts of DMF.
Practical example comparative example 3
A flame-retardant coating comprises the following raw materials in parts by weight:
330100 parts of polyether, 32 parts of TDI, 21 parts of aluminum hydroxide, 0.2 part of stannous octoate, 0.1 part of triethylene diamine, 0.3 part of tourmaline powder and 30 parts of DMF.
The flame retardant coating of the application examples 1 to 4 and the application examples 1 to 3 is prepared by the following steps: the method comprises the following steps:
(1) after the materials are mixed, the mixture is coated on polyester fabric within the operable time at the thickness of 1.0mm and the speed of 30m/min, and then the polyester fabric is baked for 1min at 160 ℃; then, the coating was applied for the second time, which was the same as the first time, and baked at 165 ℃ for 1.5 min.
(2) The accumulated dry sizing amount of the two coatings is 25 to 30g/m2。
Physical properties including hand, fastness, flame retardancy and hydrophobicity of the flame retardant coatings prepared in practical examples 1 to 4 of the present invention and practical examples 1 to 3 were measured, respectively, and the results are shown in table 1.
Table 1 physical test properties of the examples
Firstly, it can be seen from table 1 that the novel polyurea-polyurethanes of the present invention can be used both as flame retardant additives and as raw materials; and is a remarkably incombustible material when used as a raw material.
Secondly, compared with the conventional common low-toxicity flame retardant DOPO + N compound system, the novel polyurea-polyurethane has obvious flame retardant advantage, has the limit oxygen index far larger than 27, and belongs to a flame-retardant material; meanwhile, the limiting oxygen index is higher than that of the common flame retardant aluminum hydroxide.
Thirdly, the novel polyurea-polyurethane of the invention has hydrophobicity, water contact angle is more than 90 degrees, and the novel polyurea-polyurethane can be used as a coating and has certain antifouling effect.
In conclusion, compared with the existing common flame retardant, the novel polyurea-polyurethane provided by the invention not only solves the problems of poor flame retardant effect, large using amount, single function and the like of the existing flame retardant, but also has obvious advantages in flame retardant effect and better hydrophobicity; the modified siloxane is used as a raw material, takes account of the flexibility of siloxane and the rigidity of a benzene ring structure, and can ensure excellent fastness and flexibility without adding a chain extender. The material has wide market prospect and can be applied to the fields of building materials, industrial materials and the like, such as textile coatings and the like.
The test method comprises the following steps:
(1) flexibility: and judging according to hand feeling. The representation method comprises the following steps: 5 is optimal and 1 is worst.
(2) Fastness: the sample was held with both hands and rubbed back and forth 10 times with or without coating peeling off. The representation method comprises the following steps: 5 is optimal and 1 is worst.
(2) Limiting oxygen index: the flame retardancy was tested with reference to GB 8624 and 2012.
(3) Water contact angle: the test was carried out according to the method described in ASTM D7334-2008 (2013). The larger the water contact angle value, the lower the surface tension, and the more excellent the stain resistance.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (6)
1. A flame retardant polyurea-polyurethane characterized by the structural formula:
wherein n is 5 to 11.
2. A preparation method of flame-retardant polyurea-polyurethane is characterized by comprising the following steps: comprises the following steps:
(1) dissolving 1mol of DOPO and 1-1.2mol of allyl amine in 50mol of 1, 4-dioxane, adding into a flask, adding 1-2 wt% of AIBN, placing into the flask, carrying out oil bath at 70-80 ℃ for 8-12h, after the reaction is finished, carrying out reduced pressure distillation, dissolving into dichloromethane, respectively washing for 3 times with 1M sodium hydroxide aqueous solution and deionized water until the solution is neutral, separating the solution, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain an intermediate product I;
the AIBN dosage is the mass percentage of DOPO;
(2) adding 1mol of I, 1.2-1.5mol of 3-chloropropyltrimethoxysilane and 4mol of triethylamine into a flask containing 30mol of dichloromethane, stirring at room temperature for 12-18h, adding 40mol of deionized water into the mixture after the reaction is finished, separating liquid, taking an organic phase, distilling under reduced pressure, and drying in vacuum to obtain an intermediate product II;
(3) adding 1mol of II and 0.4-0.5mol of dihydroxy polysiloxane into a flask filled with 50mol of methanol, mixing, stirring, cooling to 0 ℃, adding 0.01mol of strontium hydroxide into the flask, keeping the temperature at 0 ℃ for reaction for 8-12h, filtering to remove the strontium hydroxide after the reaction is finished, adding 5-6 wt% of cation exchange resin, oscillating for 30min, filtering, removing the solvent under reduced pressure, and vacuum drying to obtain an intermediate product III;
the dosage of the cation exchange resin is the mass percent of the dihydroxy polysiloxane;
(4) placing 2mol of TDI in a flask, heating to 70-90 ℃, introducing protective gas, dissolving 1mol of III in 50mol of anhydrous organic solvent, placing in a constant pressure dropping funnel, slowly dropping into the flask, and continuously stirring for 12-24h after dropping is finished to obtain a target product IV.
3. The method of claim 2, wherein the method comprises the steps of: the polymerization degree n of the dihydroxypolysiloxane is 5-11.
4. The method of claim 2, wherein the method comprises the steps of: the cation exchange resin is WK-40, D113 or IRC-84.
5. The method of claim 2, wherein the method comprises the steps of: the protective gas is nitrogen or argon.
6. The method of claim 2, wherein the method comprises the steps of: the anhydrous organic solvent is cyclohexanone, DMF, 1, 4-dioxane or toluene.
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