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CN117801202B - High-strength high-stability high-flame-retardance polyurethane foam material without ODS (oxide dispersion medium) substances and preparation method and application thereof - Google Patents

High-strength high-stability high-flame-retardance polyurethane foam material without ODS (oxide dispersion medium) substances and preparation method and application thereof Download PDF

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CN117801202B
CN117801202B CN202311846802.XA CN202311846802A CN117801202B CN 117801202 B CN117801202 B CN 117801202B CN 202311846802 A CN202311846802 A CN 202311846802A CN 117801202 B CN117801202 B CN 117801202B
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parts
component
composite
glycol
flame retardant
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CN117801202A (en
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孟繁勤
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Henan Duolun New Materials Co ltd
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Henan Duolun New Materials Co ltd
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    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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  • Polyurethanes Or Polyureas (AREA)
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Abstract

The invention belongs to the technical field of polyurethane, and discloses a polyurethane foaming material with high strength, high stability and high flame retardance and without ODS substances, and a preparation method and application thereof. The polyurethane foaming material comprises a component A and a component B; the mass ratio of the component A to the component B is 1-1.2: 1, a step of; the component A comprises isocyanate; the component B comprises the following components in parts by weight: 70-90 parts of composite flame-retardant polyester polyol, 10-25 parts of composite polyether polyol, 1-5 parts of composite silicone oil, 5-7 parts of catalyst, 30-45 parts of composite flame retardant, 5-10 parts of foaming agent and 2-5 parts of water. According to the invention, the polyurethane foaming material with the nonflammable characteristic is obtained through compounding the composite flame retardant; the polyurethane foaming material obtained by the invention has lower heat conductivity coefficient, better fluidity, better strength and dimensional stability and lower GWP value; compared with other foaming systems, the foaming agent has higher production and application safety guarantee.

Description

High-strength high-stability high-flame-retardance polyurethane foam material without ODS (oxide dispersion medium) substances and preparation method and application thereof
Technical Field
The invention relates to the technical field of polyurethane, in particular to a polyurethane foaming material with high strength, high stability and high flame retardance and no ODS substance, and a preparation method and application thereof.
Background
The polyurethane rigid foam is a high molecular polymer prepared by mixing isocyanate and polyether serving as main raw materials under the action of a foaming agent, a catalyst, a flame retardant and other auxiliary agents through special equipment and foaming in situ through high-pressure spraying. Polyurethane foam has both soft foam and hard foam. The soft foam is of an open pore structure, and the hard foam is of a closed pore structure; soft bubbles are classified into skinning and non-skinning. And (3) spraying in a cold storage, namely polyurethane thermal insulation spraying. The cold storage spraying is a spraying technology. The closed porosity of the polyurethane hard foam body is more than or equal to 95%, the water absorption rate is less than or equal to 1%, the energy-saving and heat-insulating effects are good, the polyurethane hard foam body is a high-density closed-pore foam compound, the heat conductivity coefficient is less than or equal to 0.022W/mk (the average temperature of a cold and hot plate is 12.5 ℃), and the energy-saving effect is good. Therefore, polyurethane rigid foams have been widely developed in spray-type refrigerators.
However, the existing polyurethane rigid foam for spray-type refrigeration houses cannot meet the requirement of environmental protection, and is difficult to achieve high flame retardant effect, and particularly, controlled substances 141B specified by the Montreal protocol are also eliminated as foaming agents, and the selectivity of alternative substances is relatively narrow, so that the cost is greatly increased. The existing polyurethane rigid foam for the spray-type refrigeration house has poor tolerance and high construction difficulty; the feeding density is larger, the dimensional stability is poorer, and the maintenance cost is higher. There is therefore a need in the art to develop a polyurethane foam having the characteristics of being completely free of CFC materials, and having lower thermal conductivity, more excellent cost advantages, strength and dimensional stability, and lower GWP values.
Disclosure of Invention
The invention aims to provide a polyurethane foaming material with high strength, high stability and high flame retardance and no ODS substance, and a preparation method and application thereof, so as to solve the problems that the existing polyurethane rigid foam for a spray-type refrigeration house is inflammable, and explosion-proof equipment is required to be arranged so as to ensure the safety of the refrigeration house, and the cost is greatly increased; the problems that the fluidity of the polyurethane rigid foam for the existing spray-type refrigeration house is poor and the construction is difficult are solved; poor strength and dimensional stability and low service life.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides a polyurethane foaming material with high strength, high stability and high flame retardance and no ODS substance, which comprises a component A and a component B; the mass ratio of the component A to the component B is 1-1.2: 1, a step of; the component A comprises isocyanate; the component B comprises the following components in parts by weight: 70-90 parts of composite flame-retardant polyester polyol, 10-25 parts of composite polyether polyol, 1-5 parts of composite silicone oil, 5-7 parts of catalyst, 30-45 parts of composite flame retardant, 5-10 parts of foaming agent and 2-5 parts of water.
Preferably, the composite flame-retardant polyester polyol comprises polyethylene glycol adipate, polybutylene glycol adipate and poly epsilon-caprolactone glycol; the mass ratio of the polyethylene glycol adipate to the polybutylene glycol adipate to the poly epsilon-caprolactone glycol is 1: 1-2: 1-1.5; the composite polyether polyol comprises polypropylene glycol and polytetrahydrofuran glycol; the mass ratio of the polypropylene glycol to the polytetrahydrofuran glycol is 1-3: 1.
Preferably, the composite silicone oil comprises amino silicone oil and hydroxyl silicone oil, wherein the mass ratio of the amino silicone oil to the hydroxyl silicone oil is 2-4: 1, a step of; the catalyst comprises 1, 8-diazabicyclo undec-7-ene and/or 1, 5-diazabicyclo (4, 3, 0) non-5-ene; the foaming agent is LBA foaming agent.
Preferably, the composite flame retardant includes refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol, tetrabutyl titanate and tris (1-chloro-2-propyl) phosphate.
Preferably, the mass ratio of the refined terephthalic acid, the isopropanol, the diethylene glycol, the neopentyl glycol and the tetrabutyl titanate is 3000-4000: 1000-2000: 5000-6000: 500-1000: 0.1-1; the dosage of the tri (1-chloro-2-propyl) phosphate is 5-15% of the total mass of the refined terephthalic acid, the isopropanol, the diethylene glycol, the neopentyl glycol and the tetrabutyl titanate.
The invention also provides a preparation method of the polyurethane foaming material with high strength, high stability and high flame retardance and without ODS substances, which comprises the following steps:
(1) Mixing refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate, reacting to obtain a reactive flame retardant, and mixing the reactive flame retardant and tri (1-chloro-2-propyl) phosphate to obtain a composite flame retardant;
(2) Mixing the composite flame-retardant polyester polyol, the composite polyether polyol, the composite silicone oil, the catalyst, the composite flame retardant, the foaming agent and water to obtain a component B;
(3) Taking isocyanate as a component A; and mixing and foaming the component A and the component B to obtain the polyurethane foaming material.
Preferably, in the step (1), the reaction temperature is 160-230 ℃ and the reaction time is 1-5 h; the mixing time of the reactive flame retardant and the tri (1-chloro-2-propyl) phosphate is 1-10 min.
Preferably, in the step (2), the mixing is performed under stirring, the stirring speed of the mixing is 3000-4000 r/min, the mixing time is 10-30 min, and the mixing temperature is 20-30 ℃.
Preferably, in the step (3), the mixing foaming is performed under the condition of stirring, the stirring speed of the mixing foaming is 2000-3000 r/min, the mixing foaming time is 10-20 min, and the mixing foaming temperature is 20-30 ℃.
The invention also provides application of the polyurethane foaming material with high strength, high stability and high flame retardance and without ODS substances in a spray-type refrigeration house.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, through the compound use of the compound flame retardant, the polyurethane foaming material with the nonflammable characteristic is prepared, so that the investment of explosion-proof equipment can be avoided, and the investment cost of a spray-type refrigeration house can be obviously reduced; the polyurethane foaming material obtained by the invention has lower heat conductivity coefficient, better fluidity, better strength and dimensional stability and lower GWP value; compared with other foaming systems, the foaming agent has higher production and application safety guarantee.
Detailed Description
The invention provides a polyurethane foaming material with high strength, high stability and high flame retardance and no ODS substance, which comprises a component A and a component B; the mass ratio of the component A to the component B is 1-1.2: 1, a step of; the component A comprises isocyanate; the component B comprises the following components in parts by weight: 70-90 parts of composite flame-retardant polyester polyol, 10-25 parts of composite polyether polyol, 1-5 parts of composite silicone oil, 5-7 parts of catalyst, 30-45 parts of composite flame retardant, 5-10 parts of foaming agent and 2-5 parts of water.
In the invention, the mass ratio of the component A to the component B is preferably 1.05-1.15: 1, further preferably 1.1:1.
In the A-component of the present invention, the isocyanate includes isophorone diisocyanate or polyphenyl polymethylene polyisocyanate.
In the component B, the consumption of the composite flame-retardant polyester polyol is preferably 75-85 parts, and more preferably 78-80 parts; the amount of the composite polyether polyol is preferably 15-20 parts, more preferably 16-18 parts; the amount of the compound silicone oil is preferably 2-4 parts, and more preferably 3-3.5 parts; the amount of the catalyst is preferably 5.5 to 6.5 parts, more preferably 6 parts; the amount of the composite flame retardant is preferably 35-40 parts, more preferably 38-39 parts; the amount of the foaming agent is preferably 6 to 9 parts, more preferably 7 to 8 parts; the amount of water used is preferably 3 to 4 parts, more preferably 3.5 parts.
In the present invention, the composite flame retardant polyester polyol comprises polyethylene glycol adipate, polybutylene glycol adipate and poly epsilon-caprolactone glycol; the mass ratio of the polyethylene glycol adipate, the polybutylene adipate and the poly epsilon-caprolactone glycol is preferably 1: 1-2: 1 to 1.5, more preferably 1: 1.2-1.5: 1.2-1.4; the composite polyether polyol comprises polypropylene glycol and polytetrahydrofuran glycol; the mass ratio of polypropylene glycol to polytetrahydrofuran glycol is preferably 1-3: 1, more preferably 1.5 to 2:1.
In the invention, the composite silicone oil comprises amino silicone oil and hydroxyl silicone oil, and the mass ratio of the amino silicone oil to the hydroxyl silicone oil is preferably 2-4: 1, more preferably 2.5 to 3:1, a step of; the catalyst comprises 1, 8-diazabicyclo undec-7-ene and/or 1, 5-diazabicyclo (4, 3, 0) non-5-ene; the foaming agent is LBA foaming agent.
In the present invention, the composite flame retardant includes refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol, tetrabutyl titanate and tris (1-chloro-2-propyl) phosphate.
In the invention, the mass ratio of the refined terephthalic acid, the isopropanol, the diethylene glycol, the neopentyl glycol and the tetrabutyl titanate is preferably 3000-4000: 1000-2000: 5000-6000: 500-1000: 0.1 to 1, more preferably 3200 to 3800: 1300-1800: 5100-5500: 600-800: 0.5 to 0.8; the amount of tris (1-chloro-2-propyl) phosphate is preferably 5 to 15% by mass of the total mass of the purified terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate, and more preferably 8 to 10% by mass of the total mass of the purified terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate.
The invention also provides a preparation method of the polyurethane foaming material with high strength, high stability and high flame retardance and without ODS substances, which comprises the following steps:
(1) Mixing refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate, reacting to obtain a reactive flame retardant, and mixing the reactive flame retardant and tri (1-chloro-2-propyl) phosphate to obtain a composite flame retardant;
(2) Mixing the composite flame-retardant polyester polyol, the composite polyether polyol, the composite silicone oil, the catalyst, the composite flame retardant, the foaming agent and water to obtain a component B;
(3) Taking isocyanate as a component A; and mixing and foaming the component A and the component B to obtain the polyurethane foaming material.
In the step (1), the reaction temperature is preferably 160-230 ℃, and more preferably 180-200 ℃; the reaction time is preferably 1 to 5 hours, more preferably 2 to 4 hours; the mixing time of the reactive flame retardant and the tri (1-chloro-2-propyl) phosphate is preferably 1-10 min, and more preferably 5-8 min.
In the step (2), the mixing is carried out under the condition of stirring, and the stirring speed of the mixing is preferably 3000-4000 r/min, more preferably 3200-3500 r/min; the mixing time is preferably 10-30 min, more preferably 20-25 min; the mixing temperature is preferably 20 to 30 ℃, more preferably 22 to 28 ℃.
In the step (3), the mixed foaming is carried out under the condition of stirring, and the stirring speed of the mixed foaming is preferably 2000-3000 r/min, more preferably 2500-2800 r/min; the mixing foaming time is preferably 10-20 min, and more preferably 12-15 min; the temperature of the mixed foaming is preferably 20 to 30 ℃, more preferably 22 to 28 ℃.
The invention also provides application of the polyurethane foaming material with high strength, high stability and high flame retardance and without ODS substances in a spray-type refrigeration house.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of the composite flame retardant:
The raw materials and the dosage thereof are as follows: 300 parts of refined terephthalic acid, 100 parts of isopropanol, 550 parts of diethylene glycol, 80 parts of neopentyl glycol, 0.1 part of tetrabutyl titanate and 123.612 parts of tris (1-chloro-2-propyl) phosphate;
the preparation process comprises the following steps:
the refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate with the weight portions are reacted for 3 hours at 180 ℃ to obtain a reactive flame retardant; and adding the tri (1-chloro-2-propyl) phosphate in the weight parts into the reactive flame retardant, and mixing for 8 minutes at room temperature to obtain the composite flame retardant.
Example 2
Preparation of the composite flame retardant:
the raw materials and the dosage thereof are as follows: 350 parts of refined terephthalic acid, 120 parts of isopropanol, 500 parts of diethylene glycol, 70 parts of neopentyl glycol, 0.1 part of tetrabutyl titanate and 124.812 parts of tris (1-chloro-2-propyl) phosphate;
the preparation process comprises the following steps:
The refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate with the weight portions are reacted for 4 hours at 190 ℃ to obtain a reactive flame retardant; and adding the tri (1-chloro-2-propyl) phosphate in the weight parts into the reactive flame retardant, and mixing for 10 minutes at room temperature to obtain the composite flame retardant.
Example 3
Preparation of the composite flame retardant:
The raw materials and the dosage thereof are as follows: 400 parts of refined terephthalic acid, 180 parts of isopropanol, 520 parts of diethylene glycol, 80 parts of neopentyl glycol, 0.1 part of tetrabutyl titanate and 118.01 parts of tris (1-chloro-2-propyl) phosphate;
the preparation process comprises the following steps:
The refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate with the weight portions are reacted for 5 hours at 220 ℃ to obtain a reactive flame retardant; and adding the tri (1-chloro-2-propyl) phosphate in the weight parts into the reactive flame retardant, and mixing for 7 minutes at room temperature to obtain the composite flame retardant.
Example 4
Preparation of polyurethane foam materials:
The raw materials and the dosage thereof are as follows: 20 parts of polyethylene glycol adipate, 40 parts of polybutylene adipate, 20 parts of poly epsilon-caprolactone diol, 9 parts of polypropylene glycol, 9 parts of polytetrahydrofuran diol, 2.5 parts of amino silicone oil, 1 part of hydroxyl silicone oil, 5.5 parts of 1, 5-diazabicyclo (4, 3, 0) non-5-ene, 40 parts of the composite flame retardant obtained in example 1, 8 parts of LBA foaming agent, 4 parts of water and 166.95 parts of polyphenyl polymethylene polyisocyanate;
the preparation process comprises the following steps:
Mixing the polyethylene glycol adipate, the polybutylene glycol adipate, the poly epsilon-caprolactone glycol, the polypropylene glycol, the polytetrahydrofuran glycol, the amino silicone oil, the hydroxyl silicone oil, the 1, 5-diazabicyclo (4, 3, 0) non-5-alkene, the composite flame retardant obtained in the example 1, the LBA foaming agent and the water at room temperature for 25 minutes at the speed of 3200r/min to obtain a component B; and mixing and foaming the component B and the polyphenyl polymethylene polyisocyanate in parts by weight at room temperature at a stirring speed of 2500r/min for 15min to obtain the polyurethane foaming material.
Through detection, the compressive strength of the polyurethane foam material obtained in the embodiment is 168MPa, the core density is 43kg/m 3, the cream time of the polyurethane foam material is 3s, the gel time is 8s, and the surface drying time is 11s.
Example 5
Preparation of polyurethane foam materials:
The raw materials and the dosage thereof are as follows: 20 parts of polyethylene glycol adipate, 30 parts of polybutylene glycol adipate, 30 parts of poly epsilon-caprolactone glycol, 12 parts of polypropylene glycol, 6 parts of polytetrahydrofuran glycol, 2.5 parts of amino silicone oil, 1 part of hydroxyl silicone oil, 5.5 parts of 1, 8-diazabicyclo undec-7-ene, 40 parts of the composite flame retardant obtained in example 2, 8 parts of LBA foaming agent, 4 parts of water and 166.95 parts of polyphenyl polymethylene polyisocyanate;
the preparation process comprises the following steps:
Mixing the polyethylene glycol adipate, the polybutylene glycol adipate, the poly epsilon-caprolactone glycol, the polypropylene glycol, the polytetrahydrofuran glycol, the amino silicone oil, the hydroxyl silicone oil, the 1, 8-diazabicyclo undec-7-ene, the composite flame retardant obtained in the example 2, the LBA foaming agent and water at the room temperature at 3500r/min for 20min to obtain a component B; and mixing and foaming the component B and the polyphenyl polymethylene polyisocyanate in parts by weight at room temperature at the stirring speed of 2800r/min for 12min to obtain the polyurethane foaming material.
Through detection, the compressive strength of the polyurethane foam material obtained in the embodiment is 167MPa, the core density is 44kg/m 3, the cream time of the polyurethane foam material is 3s, the gel time is 9s, and the surface drying time is 12s.
Example 6
Preparation of polyurethane foam materials:
The raw materials and the dosage thereof are as follows: 20 parts of polyethylene glycol adipate, 30 parts of polybutylene glycol adipate, 30 parts of poly epsilon-caprolactone glycol, 15 parts of polypropylene glycol, 5 parts of polytetrahydrofuran glycol, 2.5 parts of amino silicone oil, 1 part of hydroxyl silicone oil, 5.5 parts of 1, 8-diazabicyclo undec-7-ene, 40 parts of the composite flame retardant obtained in example 3, 8 parts of LBA foaming agent, 4 parts of water and 185.15 parts of isophorone diisocyanate;
the preparation process comprises the following steps:
Mixing the polyethylene glycol adipate, the polybutylene glycol adipate, the poly epsilon-caprolactone glycol, the polypropylene glycol, the polytetrahydrofuran glycol, the amino silicone oil, the hydroxyl silicone oil, the 1, 8-diazabicyclo undec-7-ene, the composite flame retardant obtained in the example 3, the LBA foaming agent and the water at the room temperature at the speed of 3800r/min for 20min to obtain a component B; and mixing and foaming the component B and the isophorone diisocyanate in parts by weight at room temperature at a stirring speed of 3000r/min for 12min to obtain the polyurethane foaming material.
Through detection, the compressive strength of the polyurethane foam material obtained in the embodiment is 168MPa, the core density is 45kg/m 3, the milky white time of the polyurethane foam material is 4s, the gel time is 10s, and the surface drying time is 11s.
Comparative example 1
The composite flame retardant of example 4 was replaced with diethyl ethylphosphate, and the same as in example 4 was repeated.
Through detection, the compressive strength of the obtained polyurethane foaming material is 143MPa, the core density is 28kg/m 3, the cream time of the polyurethane foaming material is 2s, the gel time is 20s, and the surface drying time is 30s.
Comparative example 2
The differences from example 4 are: the addition of polyethylene adipate and polybutylene adipate was omitted and the procedure of example 4 was followed.
Through detection, the compressive strength of the obtained polyurethane foaming material is 152MPa, the core density is 30kg/m 3, the cream time of the polyurethane foaming material is 2s, the gel time is 22s, and the surface drying time is 28s.
Comparative example 3
The differences from example 4 are: the addition of polytetrahydrofuran diol was omitted and the procedure of example 4 was followed.
Through detection, the compressive strength of the obtained polyurethane foaming material is 141MPa, the core density is 26kg/m 3, the cream time of the polyurethane foaming material is 2s, the gel time is 25s, and the surface drying time is 32s.
The properties of the polyurethane foam materials obtained in examples 4 to 6 and comparative examples 1 to 3 were examined according to the following criteria, and the results are shown in Table 1.
Detection standard: measuring the density of the foaming material according to GB/T6343-2009; measuring the heat conductivity coefficient of the foaming material according to GB/T10295-2008; the bond strength, oxygen index, dimensional stability and burning properties of the foam were determined according to JC 936-2004.
As can be seen from examples 4-6, comparative examples 1-3 and Table 1, the polyurethane foam material obtained by the invention has lower heat conductivity, better fluidity, better strength and dimensional stability and lower GWP value, and the flame retardant level of the polyurethane foam material obtained is obviously improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. A polyurethane foaming material with high strength, high stability and high flame retardance, which does not contain ODS substances, the polyurethane foaming material is characterized by comprising a component A and a component B; the mass ratio of the component A to the component B is 1-1.2: 1, a step of; the component A comprises isocyanate; the component B comprises the following components in parts by weight: 70-90 parts of composite flame-retardant polyester polyol, 10-25 parts of composite polyether polyol, 1-5 parts of composite silicone oil, 5-7 parts of catalyst, 30-45 parts of composite flame retardant, 5-10 parts of foaming agent and 2-5 parts of water;
The composite flame-retardant polyester polyol comprises polyethylene glycol adipate, polybutylene glycol adipate and poly epsilon-caprolactone glycol; the mass ratio of the polyethylene glycol adipate to the polybutylene glycol adipate to the poly epsilon-caprolactone glycol is 1: 1-2: 1-1.5; the composite polyether polyol comprises polypropylene glycol and polytetrahydrofuran glycol; the mass ratio of the polypropylene glycol to the polytetrahydrofuran glycol is 1-3: 1, a step of;
The composite silicone oil comprises amino silicone oil and hydroxyl silicone oil, wherein the mass ratio of the amino silicone oil to the hydroxyl silicone oil is 2-4: 1, a step of; the catalyst comprises 1, 8-diazabicyclo undec-7-ene and/or 1, 5-diazabicyclo (4, 3, 0) non-5-ene; the foaming agent is LBA foaming agent;
the composite flame retardant comprises refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol, tetrabutyl titanate and tri (1-chloro-2-propyl) phosphate;
the preparation method of the polyurethane foam material with high strength, high stability and high flame retardance and without ODS substances comprises the following steps:
(1) Mixing refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate, reacting to obtain a reactive flame retardant, and mixing the reactive flame retardant and tri (1-chloro-2-propyl) phosphate to obtain a composite flame retardant;
(2) Mixing the composite flame-retardant polyester polyol, the composite polyether polyol, the composite silicone oil, the catalyst, the composite flame retardant, the foaming agent and water to obtain a component B;
(3) Taking isocyanate as a component A; and mixing and foaming the component A and the component B to obtain the polyurethane foaming material.
2. The polyurethane foam material with high strength, high stability and high flame retardance and without ODS substances according to claim 1, wherein the mass ratio of the refined terephthalic acid to the isopropanol to the diethylene glycol to the neopentyl glycol to the tetrabutyl titanate is 3000-4000: 1000-2000: 5000-6000: 500-1000: 0.1-1; the dosage of the tri (1-chloro-2-propyl) phosphate is 5-15% of the total mass of the refined terephthalic acid, the isopropanol, the diethylene glycol, the neopentyl glycol and the tetrabutyl titanate.
3. The method for preparing the high-strength high-stability high-flame-retardance polyurethane foam material without ODS substances according to claim 1 or 2, which is characterized by comprising the following steps:
(1) Mixing refined terephthalic acid, isopropanol, diethylene glycol, neopentyl glycol and tetrabutyl titanate, reacting to obtain a reactive flame retardant, and mixing the reactive flame retardant and tri (1-chloro-2-propyl) phosphate to obtain a composite flame retardant;
(2) Mixing the composite flame-retardant polyester polyol, the composite polyether polyol, the composite silicone oil, the catalyst, the composite flame retardant, the foaming agent and water to obtain a component B;
(3) Taking isocyanate as a component A; and mixing and foaming the component A and the component B to obtain the polyurethane foaming material.
4. The method for preparing the polyurethane foam material with high strength, high stability and high flame retardance and without ODS substances according to claim 3, wherein in the step (1), the reaction temperature is 160-230 ℃ and the reaction time is 1-5 h; the mixing time of the reactive flame retardant and the tri (1-chloro-2-propyl) phosphate is 1-10 min.
5. The method for producing a polyurethane foam material free of ODS substances having high strength, high stability and high flame retardance according to claim 4, wherein in the step (2), the mixing is carried out under stirring conditions at a stirring speed of 3000 to 4000r/min for 10 to 30min and at a temperature of 20 to 30 ℃.
6. The method for preparing the polyurethane foam material with high strength, high stability and high flame retardance and without ODS substances according to claim 4 or 5, wherein in the step (3), the mixed foaming is carried out under the condition of stirring, the stirring speed of the mixed foaming is 2000-3000 r/min, the time of the mixed foaming is 10-20 min, and the temperature of the mixed foaming is 20-30 ℃.
7. The use of the polyurethane foam material without ODS substance with high strength, high stability and high flame retardance according to claim 1 or 2 in a spray-type refrigerator.
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