CN116023614A - High-fluidity flame-retardant polyurethane soft foam composition - Google Patents

Abstract

The invention relates to the field of flexible polyurethane foam materials, and discloses a high-fluidity flame-retardant polyurethane flexible foam composition, which comprises component A and component B, and the weight ratio of component A to component B is 2:1 ～10:3; Among them, component A: 90～100 parts of polyether polyol, 0.5～1.3 parts of catalyst, 0.8～1.5 parts of foam stabilizer, 2～4 parts of blowing agent, 5～15 parts of flame retardant; Component B: diisocyanate; mix and stir the raw materials of the above component A evenly to obtain a polymer; mix component A and component B to obtain a mixed foaming material with high fluidity, pour it into a mold and mature it Polyurethane flexible foam products are obtained; the present invention uses several different types of catalysts for compounding, which effectively prolongs the milk white time, so that there is sufficient operating time when producing complex large-scale products, and the foam can release strong coagulation in the later stage. Glue activity reduces the adverse effects on foam products caused by the addition of flame retardants.

Description

A high fluidity flame retardant polyurethane flexible foam composition

technical field

The invention relates to the field of flexible polyurethane foam materials, more specifically, it relates to a high fluidity flame-retardant polyurethane flexible foam composition.

Background technique

In some foaming reactions of flexible polyurethane foam products, especially when producing foaming materials containing diphenylmethane diisocyanate or polyurethane products with complex molding shapes, in order to improve the yield of products, it is necessary to ensure that the material The viscosity cannot increase too fast in the initial stage, so that the foaming material can be evenly distributed in the mold cavity. In order to shorten the foam curing time, sometimes high-activity catalysts are used or the amount of catalysts is increased, but this will lead to problems such as too short milk white time and poor material fluidity, which will give a variety of high-performance foam products in the preparation process. posed difficulties.

Traditional strong gel tin metal catalysts are restricted in more and more export products due to potential hidden dangers in terms of biological safety and environmental protection, while alternative environmentally friendly strong gel catalysts such as organic bismuth also have a milky period Short, not resistant to hydrolysis, insufficient catalytic activity in the later stage, etc., not only cannot be prepared into composite materials to facilitate long-term storage and transportation, but also it is difficult to control all aspects of performance of foam products.

In most cases, the flame retardant of polyurethane foam needs to be mixed with some flame retardants in the polyether material, and for some liquid flame retardants with higher viscosity and solid flame retardant particles with larger particle If the amount exceeds a certain range, it will have adverse effects on the fluidity of the foamed material and the expansion ratio of the soft foam, and will also affect the mechanical properties of the foam product to a certain extent.

Publication No. CN102977316A discloses a slow-gel polyurethane soft foam composition without foam stabilizer. The fluidity of the combined material is good but the gel time is too long, which greatly reduces the production efficiency, and the produced polyurethane Soft foam cannot meet the requirements of some application fields in terms of mechanical properties and flame retardancy. Publication No. CN104558478A discloses a low-odor and highly flame-retardant automotive polyurethane interior foam and its preparation method. Its milky time is short, which is not conducive to the uniform distribution of materials throughout the mold cavity in some cases, and the foaming agent Dichloromethane is used, which will cause harm to the human body and the environment during the production process. Publication No. CN104558478A discloses an environmentally friendly flexible polyurethane foam containing castor oil. Although the cost can be reduced to a certain extent, the overall performance of the foam is poor and tin metal is used in the catalyst.

Contents of the invention

The invention provides a high fluidity flame retardant polyurethane flexible foam composition, which comprises component A and component B, and the weight ratio of component A to component B is 2:1 to 10:3;

Among them, component A: 90-100 parts of polyether polyol, 0.5-1.3 parts of catalyst, 0.8-1.5 parts of foam stabilizer, 2-4 parts of foaming agent, and 5-15 parts of flame retardant;

Component B: diisocyanate;

Mix and stir the raw materials of the above component A evenly to obtain a polymer;

Stir component A and component B at a certain speed at a temperature of 20-30°C to obtain a mixed foaming material with high fluidity, pour it into a mold and mature to obtain a polyurethane flexible foam product.

Further: the polyether polyol is a mixture of any two or more of soft foam polyether polyols, high activity polyether polyols and soft foam grafted polyether polyols with a molecular weight of 1500-3000.

Further: the polyether polyol is a flexible polyether polyol with a molecular weight of 1500-3000, a high-activity polyether polyol with a molecular weight of 5000-6500 and a grafted polyether with a styrene-acrylonitrile mixed monomer as a graft monomer The mixture of two or more kinds of polyols has a ratio of parts by weight of 5:2:2 to 3:1:1.

Further: the catalyst in component A is a mixture of high-activity gel-type amine catalysts, medium-activity amine catalysts, tin-free and hydrolysis-resistant environment-friendly metal/amine catalysts.

Further: Examples of highly active gel-type amine catalysts include, but are not limited to, triethylenediamine (A33), N,N-dimethyl-N',N'-di(2-hydroxypropyl)-1 , at least one of 3-propanediamine and the like. Other commercially available gel-type catalysts include DY-35 and DY-60 of Deyin Chemical.

Further: Moderately active amine catalysts include N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N-methylN'-hydroxyethylpiperazine, N,N-dimethyl At least one of (4-methyl-1-piperazinyl)ethylamine.

Further: the tin-free, hydrolysis-resistant, environmentally friendly metal/amine catalyst is FOCAT-8002 or FOCAT-8003M, and also includes one or more of the heat-sensitive delayed catalysts CUCAT-RM30A and CUCAT-RM30B.

Further: the parts by weight of the catalyst is 0.08-0.24 parts of high-activity gel-type amine catalyst A33 per 100 parts of polyether polyol, and the medium-activity amine catalyst N-methyl N'-hydroxyethylpiperazine 0.3 to 0.5 parts, and 0.7 to 1.2 parts for FOCAT-8003M, an environment-friendly metal/amine catalyst that does not contain tin and is resistant to hydrolysis.

Further: the foaming agent includes low-boiling hydrocarbons, water, and CO2.

Further: the foaming agent includes at least one of water, CO2, butane, pentane, and cyclopentane.

Further: the blowing agent is water.

The most preferred technical scheme in the foaming agent is to use water as the sole foaming agent of the present invention without any other foaming agents. The present invention only uses water as the foaming agent, and does not use fluorine-containing or chlorine-containing foaming agents, so that the discharge of toxic and harmful substances in the product can be reduced, air pollution will not be caused, and the product is safer and more environmentally friendly.

Further: the foam stabilizer is a polysiloxane-polyoxyalkylene copolymer.

Foam stabilizers include but are not limited to Momentive L-580, AK-8805, etc.

Further: the flame retardant includes two kinds of halogenated phosphates, phosphoric acid esters, melamine and its salts, halogenated hydrocarbons and other halogen-containing flame retardants, reactive flame retardants and inorganic flame retardants, etc. Or a combination of two or more different types of flame retardants.

Examples of halophosphates in the present invention include, but are not limited to, tris(2-chloropropyl)phosphate (TCPP), tris(2,3-dichloropropyl)phosphate (TDCP), tetrakis(2-chloro Ethyl)diethylene ether diphosphate, tetrakis(2-chloroethyl)ethylene diphosphate and tetrakis(2-chloroethyl)-2,2-dichloromethyl-1,3-ethylene One or more of propyl diphosphate.

Examples of phosphates in the present invention include, but are not limited to, dimethyl methylphosphonate (DMMP) and/or dimethyl ethylphosphonate (DEEP), Fyrol HF-4, WSFR-117HF.

Examples of melamine and its salt flame retardants in the present invention include but not limited to melamine cyanurate (MCA), melamine polyphosphate (MPP).

Further: the flame retardant in component A is: in parts by weight,

Tris (2-chloropropyl) phosphate (TCPP) 5-15 parts, tris (dichloropropyl) phosphate (TDCP) 3-12 parts, methyl methyl phosphate (DMMP) 2-10 parts, B 2-10 parts of diethyl phosphate (DEEP), 1-5 parts of melamine cyanurate (MCA) and 1-5 parts of melamine polyphosphate (MPP), and 5-20 parts of mixed reaction flame retardant WSFR-780 The diisocyanate in the component B is toluene diisocyanate or its mixture with one or more of diphenylmethane diisocyanate and modified diphenylmethane diisocyanate.

Among them, catalyst A33 is a highly active gel catalyst, which is a commercially available product and was purchased from Xuzhou Yihuiyang New Material Co., Ltd.

Among them, FOCAT-8002, a tin-free, hydrolysis-resistant, environmentally friendly metal/amine catalyst, is a highly active general-purpose foaming catalyst that can prolong the creaming time. It is a commercially available product and was purchased from Guangzhou Yourun Synthetic Materials Co., Ltd.

Among them, FOCAT-8003M, an environmentally friendly hydrolysis-resistant metal/amine catalyst that does not contain zero tin, is a catalyst suitable for MDI polyether foaming systems, which can prolong the milk white time and later curing speed. Run Synthetic Materials Co., Ltd.

The present invention also proposes a flame-retardant polyurethane flexible foam, the preparation method of which is to stir the component A and component B in the above composite material at a temperature of 20-30°C at a speed of 1200-2000r/min and stir evenly for 8 Quickly pour it into the mold after ~20s, and place it in a 60-80°C oven to fully mature for 10-24 hours after the foam stops growing.

The beneficial effects of the present invention are:

1. The high-fluidity flame-retardant polyurethane flexible foam composition proposed by the present invention improves the fluidity of the foaming composition when producing foam products without affecting the mechanical properties of the foam, and effectively prolongs the milky time, making it There is sufficient operating time for the production of complex large-scale products, and the post-aging and molding of the foam prepared by the composite material are fast, which is beneficial to improving product quality.

2. In this foam composition, the traditional organic tin catalyst is replaced by a hydrolysis-resistant environmental protection catalyst, and full water foaming is used, which is not only beneficial to the storage of the foam composition, but also meets the requirements of various foam products for volatile organic compounds. content and other environmental protection export requirements.

3. By fine-tuning the amount and ratio of the catalyst, the strong gel catalytic activity that the foam can release in the later stage reduces the disadvantages caused by the addition of flame retardants, especially a large amount of powder flame retardants, on the mechanical properties of foam products. Influence, and to a certain extent, is conducive to the improvement of flame retardant performance.

4. The flame-retardant polyurethane flexible foam composition of the present invention is an all-water foaming system, which has no damage to the ozone layer and has environmental protection advantages.

Detailed ways

The subject matter described herein will now be discussed with reference to example implementations. It should be understood that the discussion of these implementations is only to enable those skilled in the art to better understand and realize the subject matter described herein, and is not intended to limit the protection scope, applicability or examples set forth in the claims. Changes may be made in the function and arrangement of elements discussed without departing from the scope of the disclosure. Various examples may omit, substitute, or add various procedures or components as needed. Additionally, features described with respect to some examples may also be combined in other examples.

Example 1

In this embodiment, a high-fluidity flame-retardant polyurethane flexible foam composition is proposed, comprising component A and component B, and the weight ratio of component A to component B is 2:1;

Among them, component A: 90 parts of polyether polyol, 0.5 part of catalyst, 0.8 part of foam stabilizer, 2 parts of foaming agent, and 5 parts of flame retardant;

Component B: diisocyanate;

Mix and stir the raw materials of the above component A evenly to obtain a polymer;

Stir component A and component B at a certain speed at a temperature of 20°C to obtain a mixed foaming material with high fluidity, pour it into a mold and mature it to obtain a flexible polyurethane foam product.

Wherein, the polyether polyol is a mixture of any two or more of soft foam polyether polyols with a molecular weight of 1500, high activity polyether polyols and soft foam grafted polyether polyols.

Further: the polyether polyol is a soft foam polyether polyol with a molecular weight of 1500, and two of the high-activity polyether polyols with a molecular weight of 5000 and the grafted polyether polyol with styrene-acrylonitrile mixed monomers as graft monomers A mixture of two or more kinds, the ratio of parts by weight is 5:2:2.

Wherein, the catalyst in component A is a mixture of high-activity gel-type amine catalyst, medium-activity amine catalyst, tin-free and hydrolysis-resistant environment-friendly metal/amine catalyst.

Examples of highly active gel-type amine catalysts include, but are not limited to, triethylenediamine (A33), N,N-dimethyl-N',N'-di(2-hydroxypropyl)-1,3- at least one of propylenediamine and the like. Other commercially available gel-type catalysts include DY-35 and DY-60 of Deyin Chemical.

Moderately active amine catalysts include N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N-methylN'-hydroxyethylpiperazine, N,N-dimethyl(4- At least one of methyl-1-piperazinyl)ethylamine.

The environmentally friendly metal/amine catalysts that do not contain tin and are hydrolysis-resistant are FOCAT-8002 or FOCAT-8003M, and also include one or more of the heat-sensitive delayed catalysts CUCAT-RM30A and CUCAT-RM30B.

The parts by weight of the catalyst are 0.08 parts of high-activity gel-type amine catalyst A33 per 100 parts of polyether polyol, 0.3 parts of medium-activity amine catalyst N-methyl N'-hydroxyethylpiperazine, excluding Tin hydrolysis-resistant environment-friendly metal/amine catalyst FOCAT-8003M is 0.7 parts.

Blowing agents include, but are not limited to, low-boiling hydrocarbons, water, CO2, and the like. Preferably at least one of water, CO2, butane, pentane, and cyclopentane. Water is more preferred.

The most preferred technical scheme in the foaming agent is to use water as the sole foaming agent of the present invention without any other foaming agents. The present invention only uses water as the foaming agent, and does not use fluorine-containing or chlorine-containing foaming agents, so that the discharge of toxic and harmful substances in the product can be reduced, air pollution will not be caused, and the product is safer and more environmentally friendly.

The foam stabilizer is polysiloxane-polyoxyalkylene copolymer.

Foam stabilizers include but are not limited to Momentive L-580, AK-8805, etc.

Flame retardants include two or two of halogenated phosphates, phosphoric acid esters, melamine and its salts, halogenated hydrocarbons and other halogen-containing flame retardants, reactive flame retardants and inorganic flame retardants, etc. Combinations of the above different types of flame retardants.

Examples of halophosphates in the present invention include, but are not limited to, tris(2-chloropropyl)phosphate (TCPP), tris(2,3-dichloropropyl)phosphate (TDCP), tetrakis(2-chloro Ethyl)diethylene ether diphosphate, tetrakis(2-chloroethyl)ethylene diphosphate and tetrakis(2-chloroethyl)-2,2-dichloromethyl-1,3-ethylene One or more of propyl diphosphate.

Examples of phosphates in the present invention include, but are not limited to, dimethyl methylphosphonate (DMMP) and/or dimethyl ethylphosphonate (DEEP), Fyrol HF-4, WSFR-117HF.

Examples of the melamine and its salt flame retardants in the present invention include but not limited to melamine cyanurate (MCA), melamine polyphosphate (MPP).

The flame retardant in component A is: in parts by weight,

5 parts of tris(2-chloropropyl) phosphate (TCPP), 3 parts of tris(dichloropropyl) phosphate (TDCP), 2 parts of dimethyl methyl phosphate (DMMP), diethyl ethyl phosphate ( DEEP) 2 parts, 1 part of melamine cyanurate (MCA) and 1 part of melamine polyphosphate (MPP), mixed reaction type flame retardant WSFR-780 is 5, and the diisocyanate in component B is toluene diisocyanate, or Mixture with one or more of diphenylmethane diisocyanate and modified diphenylmethane diisocyanate.

Among them, catalyst A33 is a highly active gel catalyst, which is a commercially available product and was purchased from Xuzhou Yihuiyang New Material Co., Ltd.

Among them, FOCAT-8002, a tin-free, hydrolysis-resistant, environmentally friendly metal/amine catalyst, is a highly active general-purpose foaming catalyst that can prolong the creaming time. It is a commercially available product and was purchased from Guangzhou Yourun Synthetic Materials Co., Ltd.

Among them, FOCAT-8003M, a tin-free, hydrolysis-resistant and environmentally friendly metal/amine catalyst suitable for MDI polyether foaming systems, can prolong the milk white time and later curing speed. It is a commercially available product and was purchased from Guangzhou Yourun Synthetic Co., Ltd. Materials Ltd.

Example 2

In this embodiment, a high-fluidity flame-retardant polyurethane flexible foam composition is proposed, which includes component A and component B, and the weight ratio of component A to component B is 6:2;

Among them, component A: 95 parts of polyether polyol, 0.8 part of catalyst, 1.2 parts of foam stabilizer, 3 parts of foaming agent, and 10 parts of flame retardant;

Component B: diisocyanate;

Mix and stir the raw materials of the above component A evenly to obtain a polymer;

Stir component A and component B at a certain speed at a temperature of 25°C to obtain a mixed foaming material with high fluidity, pour it into a mold and mature it to obtain a flexible polyurethane foam product.

Wherein, the polyether polyol is a mixture of any two or more of soft foam polyether polyols with a molecular weight of 2500, high activity polyether polyols and soft foam grafted polyether polyols.

Further: the polyether polyol is a soft foam polyether polyol with a molecular weight of 2500, and two of the high-activity polyether polyols of 6000 and the grafted polyether polyol with styrene-acrylonitrile mixed monomers as graft monomers A mixture of two or more, the ratio of parts by weight is 4:1:1.

Wherein, the catalyst in component A is a mixture of high-activity gel-type amine catalyst, medium-activity amine catalyst, tin-free and hydrolysis-resistant environment-friendly metal/amine catalyst.

Examples of highly active gel-type amine catalysts include, but are not limited to, triethylenediamine (A33), N,N-dimethyl-N',N'-di(2-hydroxypropyl)-1,3- at least one of propylenediamine and the like. Other commercially available gel-type catalysts include DY-35 and DY-60 of Deyin Chemical.

Moderately active amine catalysts include N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N-methylN'-hydroxyethylpiperazine, N,N-dimethyl(4- At least one of methyl-1-piperazinyl)ethylamine.

The environmentally friendly metal/amine catalysts that do not contain tin and are hydrolysis-resistant are FOCAT-8002 or FOCAT-8003M, and also include one or more of the heat-sensitive delayed catalysts CUCAT-RM30A and CUCAT-RM30B.

The parts by weight of the catalyst are 0.12 parts of high-activity gel-type amine catalyst A33 per 100 parts of polyether polyol, 0.4 part of medium-activity amine catalyst N-methyl N'-hydroxyethylpiperazine, excluding Tin hydrolysis-resistant environmental protection metal/amine catalyst FOCAT-8003M is 0.9 parts.

Blowing agents include, but are not limited to, low-boiling hydrocarbons, water, CO2, and the like. Preferably at least one of water, CO2, butane, pentane, and cyclopentane. Water is more preferred.

The most preferred technical scheme in the foaming agent is to use water as the sole foaming agent of the present invention without any other foaming agents. The present invention only uses water as the foaming agent, and does not use fluorine-containing or chlorine-containing foaming agents, so that the discharge of toxic and harmful substances in the product can be reduced, air pollution will not be caused, and the product is safer and more environmentally friendly.

The foam stabilizer is polysiloxane-polyoxyalkylene copolymer.

Foam stabilizers include but are not limited to Momentive L-580, AK-8805, etc.

Flame retardants include two or two of halogenated phosphates, phosphoric acid esters, melamine and its salts, halogenated hydrocarbons and other halogen-containing flame retardants, reactive flame retardants and inorganic flame retardants, etc. Combinations of the above different types of flame retardants.

Examples of halophosphates in the present invention include, but are not limited to, tris(2-chloropropyl)phosphate (TCPP), tris(2,3-dichloropropyl)phosphate (TDCP), tetrakis(2-chloro Ethyl)diethylene ether diphosphate, tetrakis(2-chloroethyl)ethylene diphosphate and tetrakis(2-chloroethyl)-2,2-dichloromethyl-1,3-ethylene One or more of propyl diphosphate.

Examples of phosphates in the present invention include, but are not limited to, dimethyl methylphosphonate (DMMP) and/or dimethyl ethylphosphonate (DEEP), Fyrol HF-4, WSFR-117HF.

Examples of the melamine and its salt flame retardants in the present invention include but not limited to melamine cyanurate (MCA), melamine polyphosphate (MPP).

The flame retardant in component A is: in parts by weight,

10 parts of tris (2-chloropropyl) phosphate (TCPP), 8 parts of tris (dichloropropyl) phosphate (TDCP), 6 parts of dimethyl methyl phosphate (DMMP), diethyl ethyl phosphate ( DEEP) 6 parts, 3 parts of melamine cyanurate (MCA) and 3 parts of melamine polyphosphate (MPP), mixed reaction flame retardant WSFR-780 is 12 parts, and the diisocyanate in component B is toluene diisocyanate, or Mixture with one or more of diphenylmethane diisocyanate and modified diphenylmethane diisocyanate.

Among them, catalyst A33 is a highly active gel catalyst, which is a commercially available product and was purchased from Xuzhou Yihuiyang New Material Co., Ltd.

Among them, FOCAT-8002, a tin-free, hydrolysis-resistant, environmentally friendly metal/amine catalyst, is a highly active general-purpose foaming catalyst that can prolong the creaming time. It is a commercially available product and was purchased from Guangzhou Yourun Synthetic Materials Co., Ltd.

Among them, FOCAT-8003M, a tin-free, hydrolysis-resistant and environmentally friendly metal/amine catalyst suitable for MDI polyether foaming systems, can prolong the milk white time and later curing speed. It is a commercially available product and was purchased from Guangzhou Yourun Synthetic Co., Ltd. Materials Ltd.

Example 3

In this embodiment, a high-fluidity flame-retardant polyurethane flexible foam composition is proposed, which includes component A and component B, and the weight ratio of component A to component B is 10:3;

Among them, component A: 100 parts of polyether polyol, 1.3 parts of catalyst, 1.5 parts of foam stabilizer, 4 parts of foaming agent, and 15 parts of flame retardant;

Component B: diisocyanate;

Mix and stir the raw materials of the above component A evenly to obtain a polymer;

Stir component A and component B at a certain speed at a temperature of 30°C to obtain a mixed foaming material with high fluidity, and pour it into a mold for aging to obtain a flexible polyurethane foam product.

Wherein, the polyether polyol is a mixture of any two or more of soft foam polyether polyols with a molecular weight of 3000, high activity polyether polyols and soft foam grafted polyether polyols.

Further: the polyether polyol is a soft foam polyether polyol with a molecular weight of 3000, and two of the high-activity polyether polyols with a molecular weight of 6500 and the grafted polyether polyol with styrene-acrylonitrile mixed monomers as graft monomers A mixture of two or more, the ratio of parts by weight is 3:1:1.

Wherein, the catalyst in component A is a mixture of high-activity gel-type amine catalyst, medium-activity amine catalyst, tin-free and hydrolysis-resistant environment-friendly metal/amine catalyst.

Examples of highly active gel-type amine catalysts include, but are not limited to, triethylenediamine (A33), N,N-dimethyl-N',N'-di(2-hydroxypropyl)-1,3- at least one of propylenediamine and the like. Other commercially available gel-type catalysts include DY-35 and DY-60 of Deyin Chemical.

Moderately active amine catalysts include N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N-methylN'-hydroxyethylpiperazine, N,N-dimethyl(4- At least one of methyl-1-piperazinyl)ethylamine.

The environmentally friendly metal/amine catalysts that do not contain tin and are hydrolysis-resistant are FOCAT-8002 or FOCAT-8003M, and also include one or more of the heat-sensitive delayed catalysts CUCAT-RM30A and CUCAT-RM30B.

The parts by weight of the catalyst are 0.24 parts of high-activity gel-type amine catalyst A33 per 100 parts of polyether polyol, 0.5 part of medium-activity amine catalyst N-methyl N'-hydroxyethylpiperazine, excluding Tin hydrolysis-resistant environmental protection metal/amine catalyst FOCAT-8003M is 1.2 parts.

Blowing agents include, but are not limited to, low-boiling hydrocarbons, water, CO2, and the like. Preferably at least one of water, CO2, butane, pentane, and cyclopentane. Water is more preferred.

The most preferred technical scheme in the foaming agent is to use water as the sole foaming agent of the present invention without any other foaming agents. The present invention only uses water as the foaming agent, and does not use fluorine-containing or chlorine-containing foaming agents, so that the discharge of toxic and harmful substances in the product can be reduced, air pollution will not be caused, and the product is safer and more environmentally friendly.

The foam stabilizer is polysiloxane-polyoxyalkylene copolymer.

Foam stabilizers include but are not limited to Momentive L-580, AK-8805, etc.

Flame retardants include two or two of halogenated phosphates, phosphoric acid esters, melamine and its salts, halogenated hydrocarbons and other halogen-containing flame retardants, reactive flame retardants and inorganic flame retardants, etc. Combinations of the above different types of flame retardants.

Examples of halophosphates in the present invention include, but are not limited to, tris(2-chloropropyl)phosphate (TCPP), tris(2,3-dichloropropyl)phosphate (TDCP), tetrakis(2-chloro Ethyl)diethylene ether diphosphate, tetrakis(2-chloroethyl)ethylene diphosphate and tetrakis(2-chloroethyl)-2,2-dichloromethyl-1,3-ethylene One or more of propyl diphosphate.

Examples of phosphates in the present invention include, but are not limited to, dimethyl methylphosphonate (DMMP) and/or dimethyl ethylphosphonate (DEEP), Fyrol HF-4, WSFR-117HF.

Examples of the melamine and its salt flame retardants in the present invention include but not limited to melamine cyanurate (MCA), melamine polyphosphate (MPP).

The flame retardant in component A is: in parts by weight,

15 parts of tris (2-chloropropyl) phosphate (TCPP), 12 parts of tris (dichloropropyl) phosphate (TDCP), 10 parts of dimethyl methyl phosphate (DMMP), diethyl ethyl phosphate ( DEEP) 10 parts, 5 parts of melamine cyanurate (MCA) and 5 parts of melamine polyphosphate (MPP), mixed reaction flame retardant WSFR-780 is 20 parts, and the diisocyanate in component B is toluene diisocyanate, or Mixture with one or more of diphenylmethane diisocyanate and modified diphenylmethane diisocyanate.

Among them, catalyst A33 is a highly active gel catalyst, which is a commercially available product and was purchased from Xuzhou Yihuiyang New Material Co., Ltd.

Among them, FOCAT-8002, a tin-free, hydrolysis-resistant, environmentally friendly metal/amine catalyst, is a highly active general-purpose foaming catalyst that can prolong the creaming time. It is a commercially available product and was purchased from Guangzhou Yourun Synthetic Materials Co., Ltd.

Among them, FOCAT-8003M, a tin-free, hydrolysis-resistant and environmentally friendly metal/amine catalyst suitable for MDI polyether foaming systems, can prolong the milk white time and later curing speed. It is a commercially available product and was purchased from Guangzhou Yourun Synthetic Co., Ltd. Materials Ltd.

Example 4

The present invention also proposes a flame-retardant polyurethane flexible foam, the preparation method of which is to stir the component A and component B in the above composite material at a temperature of 20-30°C at a speed of 1200-2000r/min and stir evenly for 8 Quickly pour it into the mold after ~20s, and place it in a 60-80°C oven to fully mature for 10-24 hours after the foam stops growing.

In the following examples:

The density of polyurethane foam is tested according to GB-T 6343-2009 "Determination of Apparent Density of Foam Plastics and Rubber".

Compression set according to GB-T 6669-2001 "Determination of compression set of soft foam polymer materials".

Tensile strength and elongation are tested according to GB-T 6344-2008 "Determination of Tensile Strength and Elongation at Break of Flexible Foam Polymers".

Resilience rate is tested according to GB-T 6670-1997 "Determination of Resilience Properties of Flexible Polyurethane Foam Plastics".

The limiting oxygen index is tested according to GB-T 2406-93 "Test Method for Combustion Performance of Plastics Oxygen Index Method".

The combustion performance is tested in accordance with GB-T 8332 "Foamed Plastics Horizontal Combustion Test".

The polyether polyol DEP-5631D used in the combined material was purchased from Shandong Bluestar Dongda Chemical Co., Ltd. The hydroxyl value of the polyether polyol is 540-557.5 mgKOH/g, the viscosity is 450-650 mPa.s (25°C), the functionality is 3, and the number average molecular weight is 3000.

Toluene diisocyanate (TDI) is TDI-80 of Blue Star Chemical Co., Ltd.

Polymethyl polyphenyl polyisocyanate (PAPI) is PM-200 of Ningbo Wanhua Polyurethane Co., Ltd.

Flame retardants DEEP, DMMP and TCPP were purchased from Wuhan Carlos Technology Co., Ltd. Flame retardants MCA and MPP were purchased from Dongguan Jiaxin New Material Co., Ltd. Phosphate ester flame retardants Fyrol HF-4 and WSFR-117HF were purchased from Zhejiang Wansheng Co., Ltd.

Catalysts N-ethylmorpholine and N-methyl N'-hydroxyethylpiperazine were purchased from Shanghai Macklin Biochemical Technology Co., Ltd.

Example 5

In the present embodiment, a high fluidity flame retardant polyurethane flexible foam composition is proposed, by weight fraction, its components are as follows:

Component A: 80 parts of polyether polyol DEP-5631D, 20 parts of polyether polyol DEP-330NG, 3.3 parts of deionized water, 0.12 parts of A33, 0.4 parts of N-ethylmorpholine, FOCAT- 8003M is 0.9 parts, L-580 is 1 part, flame retardant DMMP and MCA are 8 parts and 3 parts respectively.

Component B: TDI is 42 parts.

Preparation of flame retardant polyurethane soft foam: According to the formula listed in Table 1, mix component A thoroughly at room temperature for 5-10 minutes, then stir with component B at 1400rpm for 8-15s at 20-30°C and then quickly Pour it into the mold, and after the foam stops growing, place it in an environment of 60-80°C for 10-24 hours to fully mature to obtain a polyurethane soft foam product with a density of 38.6kg/m3, and its properties are shown in Table 3.

Example 6

In the present embodiment, a high fluidity flame retardant polyurethane flexible foam composition is proposed, by weight fraction, its components are as follows:

Component A: 80 parts of polyether polyol DEP-5631D, 20 parts of polyether polyol DEP-330NG, 3.3 parts of deionized water, 0.12 parts of A33, N-methyl N'-hydroxyethyl piperazine 0.32 parts for FOCAT-8003M, 0.9 parts for FOCAT-8003M, 1 part for AK-8805, 8 parts and 3 parts for flame retardant DEEP and MCA respectively.

Component B: TDI is 42 parts.

Preparation of flame retardant polyurethane soft foam: According to the formula listed in Table 1, mix component A thoroughly at room temperature for 5-10 minutes, then stir with component B at 1400rpm for 8-15s at 20-30°C and then quickly Pour it into a mold, and after the foam stops growing, place it in an environment of 60-80°C for 10-24 hours to fully mature to obtain a polyurethane soft foam product with a density of 42.7kg/m3, and its properties are shown in Table 3.

Example 7

In the present embodiment, a high fluidity flame retardant polyurethane flexible foam composition is proposed, by weight fraction, its components are as follows:

Component A: 70 parts of polyether polyol DEP-5631D, 30 parts of polyether polyol DEP-330NG, 3.3 parts of deionized water, 0.12 parts of A33, 0.40 parts of N-ethylmorpholine, FOCAT- 8002 is 0.85 parts, L-580 is 1 part, flame retardant TCPP and Fyrol HF-4 are 15 parts and 5 parts respectively.

Component B: 30 parts of TDI, 18 parts of PAPI, see Table 1 for the specific formula.

Preparation of flame retardant polyurethane soft foam: According to the formula listed in Table 1, mix component A thoroughly at room temperature for 5-10 minutes, then stir with component B at 1400rpm for 8-15s at 20-30°C and then quickly Pour it into a mold, and after the foam stops growing, place it in an environment of 60-80°C for 10-24 hours to fully mature to obtain a polyurethane flexible foam product with a density of 41.4kg/m3, and its properties are shown in Table 3.

Table 1 embodiment formula (the content of component is in mass parts)

Table 2 The formula of existing polyurethane combination material

The performance contrast parameter of the flexible polyurethane foam that table 3 embodiment and existing combination foaming material make

Test items Contrast 1 Contrast 2 Example 5 Example 6 Example 7 Free density (kg/m3) 40.0 37.2 38.6 42.7 41.4 Cream time (s) 12 15 20 twenty two 19 Debonding time (s) 120 119 105 109 111 Compression set (KPa) 9.8 11.3 9.6 10.1 9.2 Tensile strength (Mpa) 98 105 103 107 122 Elongation% 240 232 238 253 260 F% 75 79 92 88 82 Rebound% 46 42 55 48 37 Limiting Oxygen Index% 24.3 23.5 27.8 26.0 28.2 Flame retardant performance≤mm/min √ √ √ √ √

Note: "√" indicates that the flame retardant performance is ≤100mm/min measured according to the standard GB/T8332.

It can be seen from the data in Table 3 that the compositions prepared in Examples 5-7 effectively prolong the creaming time, and the debonding of the foam is accelerated, and the mechanical properties and flame retardancy of the foam are maintained at the original level or slightly improved. While giving sufficient operating time to foam products, it also increases the controllability of its quality

The above embodiment of this embodiment has been described, but this embodiment is not limited to the above-mentioned specific implementation, the above-mentioned specific implementation is only illustrative, not restrictive, and those of ordinary skill in the art will Inspired by the embodiment, without departing from the gist of the embodiment and the protection scope of the claims, many forms can be made, all of which are within the protection of the embodiment.

Claims (10)

1. The high-fluidity flame-retardant polyurethane soft foam composition is characterized by comprising a component A and a component B, wherein the weight ratio of the component A to the component B is 2:1-10:3;

wherein, component A: 90-100 parts of polyether polyol, 0.5-1.3 parts of catalyst, 0.8-1.5 parts of foam stabilizer, 2-4 parts of foaming agent and 5-15 parts of flame retardant;

component B: a diisocyanate;

mixing and stirring all the raw materials of the component A uniformly to obtain a polymer;

and (3) stirring the component A and the component B at a certain speed at the temperature of 20-30 ℃ to obtain a mixed foaming material with high fluidity, and pouring the mixed foaming material into a mould for curing to obtain the polyurethane soft foam product.

2. The high-fluidity flame-retardant polyurethane soft foam composition according to claim 1, wherein the polyether polyol is a mixture of any two or more of a soft foam polyether polyol having a molecular weight of 1500 to 3000, a high-activity polyether polyol and a soft foam graft polyether polyol.

3. The high-fluidity flame-retardant polyurethane soft foam composition according to claim 2, wherein the polyether polyol is a mixture of two or more of a soft foam polyether polyol having a molecular weight of 1500 to 3000, a high-activity polyether polyol having a molecular weight of 5000 to 6500 and a graft polyether polyol having a styrene-acrylonitrile mixed monomer as a graft monomer in a weight ratio of 5:2:2 to 3:1:1.

4. The high-fluidity flame-retardant polyurethane soft foam composition according to claim 1, wherein the catalyst in the component A is a mixture of high-activity gel-type amine catalyst, medium-activity amine catalyst, tin-free hydrolysis-resistant environment-friendly metal/amine catalyst.

5. A high flow flame retardant polyurethane soft foam composition according to claim 4, wherein examples of the high activity gel type amine catalyst include, but are not limited to, at least one of triethylenediamine (a 33), N-dimethyl-N ', N' -bis (2-hydroxypropyl) -1, 3-propanediamine, and the like. Other commercially available gel catalysts also include DY-35, DY-60, etc. of Desmochemical.

6. The high flow flame retardant polyurethane soft foam composition of claim 4, wherein the medium activity amine catalyst comprises at least one of N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N-methyl N' -hydroxyethylpiperazine, N-dimethyl (4-methyl-1-piperazinyl) ethylamine.

7. The high flow flame retardant polyurethane foam composition of claim 4, wherein the tin-free hydrolysis resistant environmentally friendly metal/amine catalyst is FOCAT-8002 or FOCAT-8003M, and further comprising one or more of the thermosensitive delay catalysts CUCAT-RM30A, CUCAT-RM 30B.

8. The high-fluidity flame-retardant polyurethane soft foam composition according to claim 1, wherein the catalyst comprises, by weight, 0.08-0.24 part of a high-activity gel-type amine catalyst A33 and 0.3-0.5 part of a medium-activity amine catalyst N-methyl N' -hydroxyethyl piperazine per 100 parts of polyether polyol, and 0.7-1.2 parts of a tin-free hydrolysis-resistant environment-friendly metal/amine catalyst FOCAT-8003M.

9. A high flow flame retardant polyurethane foam composition according to claim 1 wherein the blowing agent comprises a low boiling hydrocarbon, water, CO2.

10. A high flow flame retardant polyurethane foam composition according to claim 9 wherein the blowing agent comprises at least one of water, CO2, butane, pentane, cyclopentane.