Organic phosphate flame retardant, preparation method and flame-retardant polymer material containing organic phosphate

Abstract

The present disclosure provides an organic phosphate flame retardant, a preparation method and a flame-retardant polymer material containing the organic phosphate. The organic phosphate flame retardant provided in the present disclosure comprises a component A and a component B, wherein the component A is selected from at least one of compounds as presented by formula (I), and the component B is selected from at least one of compounds as presented by formula (II). In formula (I), R1 and R2 are a C1-C6 alkyl, and R3 is a C1-C8 alkyl. In formula (II), R4 is methyl or ethyl, and R5 and R6 are a C1-C8 alkyl. When the organic phosphate flame retardant is applied to polyurethane foaming, a polyurethane raw material polyether can be endowed with good storage stability, and the polyurethane material can also be endowed with good flame-retardant stability and dimensional stability by the organic phosphate flame retardant.

Description

Organic phosphate flame retardant, preparation method and flame retardant polymer material containing the organic phosphate

[0001] Cross-references to related publications

[0002] The present disclosure claims priority to Chinese Patent No. 2024102284938, filed on February 29, 2024, entitled “Organophosphate flame retardant, preparation method and flame retardant polymer material containing the same,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to the technical field of flame retardant materials, and in particular to an organophosphate flame retardant, a preparation method, and a flame retardant polymer material containing the organophosphate. Background Art

[0004] Polyurethane materials are widely used in the automotive, home appliance, and building materials industries due to their excellent electrical and mechanical properties, acid and alkali resistance, and adhesion. However, polyurethane materials are highly flammable in air and decompose to produce large amounts of toxic fumes, which can cause fires and casualties. Consequently, flame retardancy, particularly halogen-free flame retardancy, is required in many fields and applications, such as building insulation, automotive interiors, and home decoration.

[0005] Generally, flame retardancy of polyurethane can be achieved by directly adding flame retardants to polyurethane materials. Common flame retardants used for polyurethane are phosphates, such as tris(1-chloro-2-propyl) phosphate (TCPP), tris(chloroethyl) phosphate (TCEP), triethyl phosphate (TEP) and dimethyl methyl phosphate (DMMP). Such phosphates have high flame retardant efficiency and are easy to process and use. They are widely used in many polyurethane materials, such as soft polyurethane foam, rigid polyurethane foam, polyurethane elastomers and polyurethane coatings.

[0006] However, traditional phosphate ester flame retardants, such as TCPP and TCEP, still contain halogens and cannot meet the current flame retardancy requirements for halogen-free polymer materials. Other common halogen-free phosphate esters, such as TEP, have poor stability in polyurethane raw material polyethers. After prolonged storage and subsequent foaming, the acid value of TEP increases due to acid hydrolysis, which affects the foaming of the polyurethane. Furthermore, polyurethane foam materials retarded with phosphate esters such as TEP experience a decrease in flame retardancy after long-term use. Simultaneously, the dimensional stability of the resulting polyurethane foam decreases, making it prone to warping, deformation, and elongation. Therefore, developing a phosphate ester flame retardant, particularly a halogen-free phosphate ester flame retardant, with excellent storage stability and minimal impact on the polyurethane foaming process, as well as the flame retardancy and dimensional stability of the polyurethane foam, remains a pressing issue for the polyurethane industry.

[0007] In view of this, the present disclosure is proposed. Summary of the Invention

[0008] The purpose of the present disclosure includes overcoming the defects of the above-mentioned prior art and providing an organic phosphate flame retardant, a preparation method and a flame retardant polymer material containing the organic phosphate.

[0009] The present disclosure can solve its technical problems by adopting the following technical solutions.

[0010] The present disclosure provides an organophosphate flame retardant, which comprises a component A and a component B, wherein the component A is selected from at least one compound represented by formula (I), and the component B is selected from at least one compound represented by formula (II):

[0011] In formula (I), R1 and R2 are C1-C6 alkyl groups, and R3 is C1-C8 alkyl groups;

[0012] In formula (II), R4 is a methyl group or an ethyl group, and R5 and R6 are C1-C8 alkyl groups.

[0013] In some optional embodiments, in formula (I), R1 and R2 are each independently selected from a linear or branched C1-C6 alkyl group, R1 and R2 may be the same or different, and R3 is selected from a linear or branched C1-C8 alkyl group; in formula (II), R4 is methyl or ethyl, R5 and R6 are each independently selected from a linear or branched C1-C8 alkyl group, and R5 and R6 may be the same or different.

[0014] In some optional embodiments, the weight proportions of component A and component B in the organic phosphate flame retardant in the composition are: component A: 90.0 wt% to 99.99 wt%, component B: 0.01 wt% to 10.0 wt%.

[0015] In some optional embodiments, the water content in component A is less than 0.3% by weight; and the water content in component B is less than 0.3% by weight.

[0016] In some optional embodiments, the moisture content of the organophosphate flame retardant is less than 0.3% by weight. The present disclosure also provides a method for preparing the above-mentioned organophosphate flame retardant, comprising: synthesizing component A using dialkylphosphinate chloride and an alkyl alcohol as raw materials, and then mixing component A and component B to obtain the organophosphate flame retardant. In some optional embodiments, component A is prepared by synthesizing dialkylphosphinate chloride and an alkyl alcohol at 40°C to 200°C.

[0017] In some optional embodiments, the synthesis temperature is 40°C to 150°C.

[0018] The present disclosure also provides a flame-retardant polymer material, which includes the above-mentioned organic phosphate flame retardant and a polymer matrix material.

[0019] In some optional embodiments, the polymer matrix material includes at least one of polyurethane, unsaturated polyester resin, epoxy resin, polycarbonate, polyester, polyphenylene ether, polyvinyl chloride and polyacrylic acid.

[0020] In some optional embodiments, the polymer matrix material is selected from polyurethane, epoxy resin or unsaturated polyester resin.

[0021] In some optional embodiments, the weight proportions of the organic phosphate flame retardant and the polymer matrix material in the flame retardant polymer material are: organic phosphate flame retardant: 5wt% to 40wt%, polymer matrix material: 60wt% to 95wt% respectively.

[0022] In some optional embodiments, the flame retardant polymer material further includes one or more of a functional additive and a flame retardant X.

[0023] In some optional embodiments, the functional additives include at least one of a reinforcing agent, an anti-dripping agent, a stabilizer, a pigment, a carbon-forming catalyst, a dispersant, a nucleating agent, an inorganic filler, an organic filler, an antioxidant and an antibacterial agent, and the mass content of the functional additives in the flame retardant polymer material is 5% to 40%.

[0024] In some optional embodiments, the flame retardant X is selected from at least one of a phosphorus-based flame retardant and a nitrogen-based flame retardant, and the mass content of the flame retardant X in the flame retardant polymer material is 0.1% to 10%.

[0025] In some optional embodiments, the phosphorus-based flame retardant includes at least one of a phosphate ester and a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative.

[0026] In some optional embodiments, the nitrogen-based flame retardant includes at least one of melamine cyanurate, melamine polyphosphate, and etherified melamine formaldehyde resin.

[0027] The beneficial effects of the present disclosure include:

[0028] The organophosphate flame retardant provided herein comprises specific components A and B. When used in polyurethane foaming, this organophosphate flame retardant imparts good storage stability to the polyether raw material of the polyurethane, and can also impart good flame retardant stability and dimensional stability to the polyurethane material. Furthermore, the organophosphate flame retardant provided herein can also be used in polymer matrix materials such as unsaturated polyesters, epoxy resins, polycarbonates, polyesters, polyphenylene ethers, polyvinyl chloride, and polyacrylic acids, providing flame retardant and fireproofing properties. DETAILED DESCRIPTION

[0029] To make the purpose, technical solutions, and advantages of the embodiments of the present disclosure more clear, the technical solutions in the embodiments of the present disclosure are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer were followed. Reagents or instruments used where the manufacturer is not specified are conventional products that can be purchased commercially.

[0030] The following describes the organic phosphate flame retardant, preparation method, and flame retardant polymer material containing the organic phosphate provided in the embodiments of the present disclosure.

[0031] In a first aspect, an embodiment of the present disclosure provides an organophosphate flame retardant, comprising component A and component B, wherein component A is selected from at least one compound represented by formula (I), and component B is selected from at least one compound represented by formula (II):

[0032] In formula (I), R1 and R2 are C1-C6 alkyl groups, and R3 is C1-C8 alkyl groups;

[0033] In formula (II), R4 is a methyl group or an ethyl group, and R5 and R6 are C1-C8 alkyl groups.

[0034] In some optional embodiments, in formula (I), R1 and R2 can be independently selected from a linear or branched C1-C6 alkyl group, and R1 and R2 can be the same or different. R3 can be selected from a linear or branched C1-C8 alkyl group.

[0035] In some optional embodiments, in formula (II), R4 is methyl or ethyl. R5 and R6 are each independently selected from a linear or branched C1-C8 alkyl group, and R5 and R6 can be the same or different.

[0036] The above-mentioned organophosphate components A and B also contain a certain amount of water. In some optional embodiments, by weight, the water content in component A is less than 0.3%; the water content in component B is less than 0.3%; further, the water content in component A is less than 0.1%, the water content in component B is less than 0.2%; and the water content in the organophosphate is less than 0.3%; further, the water content in the organophosphate is less than 0.1%. Higher water content can affect the use of the dry organophosphate, for example, causing abnormalities in the polyurethane foaming process.

[0037] In a second aspect, the embodiments of the present disclosure further provide a method for preparing the above-mentioned organophosphate flame retardant, comprising: synthesizing component A using dialkyl hypophosphite chloride and alkyl alcohol as raw materials, and then mixing component A and component B to obtain the organophosphate flame retardant.

[0038] In some optional embodiments, the present disclosure provides a method for preparing the above-mentioned component A: dialkylphosphinate chloride and alkyl alcohol are directly synthesized at 40° C. to 200° C.;

[0039] A catalyst may be used or not; when a catalyst is used, the catalyst is preferably an organic amine.

[0040] In some optional embodiments, the catalyst may include an amine catalyst, such as at least one of triethylamine, triethanolamine, and N,N-dimethyl-p-toluidine.

[0041] When the synthesis temperature during the preparation of the above-mentioned component A is lower than 40°C, the reaction rate is slow; when the temperature is higher than 200°C, the raw materials are easily oxidized, causing the final product to be yellow in color.

[0042] In some optional embodiments, the reaction temperature is 40°C to 150°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or any value between 40°C and 150°C or any range therebetween.

[0043] In a third aspect, the present disclosure further discloses a flame-retardant polyurethane material, which contains the above-mentioned organophosphate flame retardant, and the organophosphate flame retardant plays a flame-retardant and fire-proof role in the polyurethane material.

[0044] The inventors have creatively discovered that by adding a mixture of organophosphate esters containing components A and B to polyether, a raw material for polyurethane, the resulting polyether can be stored for long periods of time without affecting the foaming process. Furthermore, polyurethane foam containing the organophosphate flame retardant components A and B exhibits excellent dimensional stability after prolonged use, without shrinking, warping, or deterioration in surface smoothness. In contrast, polyurethane foam containing only component A exhibits poor flame retardancy, requiring the addition of a small amount of component B to improve its flame retardancy. Specifically, the weight percentage ratio of component A to component B is (90-99.99):(0.01-10). Surprisingly, the inventors have also unexpectedly discovered that adding a small amount of component B to component A can improve the properties of the resulting polyurethane foam, such as improving the uniformity of its cells and the smoothness of the polyurethane foam surface. However, when the amount of component B added is too high, the storage stability of the organophosphate flame retardant in the polyether deteriorates, affecting the polyurethane foaming process and causing abnormalities such as scorching and yellowing of the polyurethane.

[0045] In some optional embodiments, the organophosphate flame retardant disclosed herein can be applied to a polyurethane material, wherein the polyurethane material comprises 5 to 40 wt% of the organophosphate flame retardant and 60 to 95 wt% of a polyurethane matrix material. The polyurethane matrix material is a polymer synthesized from a polyol, an isocyanate, and a chain extender, such as at least one selected from polyester polyurethane, polyether polyurethane, polycarbonate polyurethane, and polycaprolactone polyurethane. If the amount of organophosphate flame retardant added is too low, the flame retardant effect will not be achieved; if the amount is too high, other properties of the flame retardant material may be affected, such as reducing the tensile and flexural properties of the flame retardant material.

[0046] In some optional embodiments, the flame retardant polymer material may include 5 wt% to 35 wt% of an organic phosphate flame retardant and 65 wt% to 95 wt% of a polyurethane matrix material.

[0047] In some optional embodiments, the mass content of the organophosphate flame retardant in the flame retardant polymer material is independently selected from any value selected from 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, or any range therebetween. Specifically, the amount of the organophosphate flame retardant used depends on the structure of the polymer matrix material.

[0048] In actual use, it has also been found that the above-mentioned organic phosphate flame retardant can also be applied to polymer matrix materials such as unsaturated polyester resin, epoxy resin, polycarbonate, polyester, polyphenylene ether, polyvinyl chloride and polyacrylic acid to play a flame retardant and fireproof role.

[0049] When organic phosphate is used in these polymer matrix materials, the flame retardant material may include 5 wt% to 40 wt% of organic phosphate flame retardant and 60 wt% to 95 wt% of the polymer matrix material.

[0050] In some optional embodiments, the polymer matrix material in the flame retardant polymer material is unsaturated polyester resin, epoxy resin or polyurethane.

[0051] When the composition consisting of component A and component B is actually used in a polymer matrix material, it can be mixed in advance and then added to the polymer matrix material or its precursor, or it can be added to the polymer matrix material or its precursor separately. Finally, the prepared flame retardant polymer matrix material contains the composition consisting of component A and component B.

[0052] In some optional embodiments, when the organic phosphate is used in a polymer matrix material such as polyurethane, unsaturated polyester resin, epoxy resin, polycarbonate, polyester, polyphenylene ether, polyvinyl chloride, and polyacrylic acid, the flame retardant material further includes a functional additive. The functional additive may include, for example, at least one of a reinforcing agent, an anti-dripping agent, a stabilizer, a pigment, a carbonization catalyst, a dispersant, a nucleating agent, an inorganic filler, an organic filler, an antioxidant, and an antibacterial agent.

[0053] In some optional embodiments, the mass content of the functional additive in the flame retardant polymer material is 5% to 40%, such as any value among 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40% or any range between two values.

[0054] In some optional embodiments, the flame retardant polymer material further includes another flame retardant X. The flame retardant X can be selected from at least one of a phosphorus-based flame retardant and a nitrogen-based flame retardant.

[0055] In some optional embodiments, the phosphorus-based flame retardant may be selected from at least one of phosphate esters and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives.

[0056] In some optional embodiments, the phosphate ester may be a cyclic phosphate CU, and the DOPO derivative may be at least one of 6H-dibenzo[c,e][1,2]oxane-6,6'-(1,4-ethanediyl)bis-6,6'dioxide and 6H-dibenzo[c,e][1,2]oxane-6,6'-(1,4-phenylethanediyl)bis-6,6'dioxide.

[0057] In some optional embodiments, the nitrogen-based flame retardant may be selected from at least one of melamine cyanurate, melamine polyphosphate, and etherified melamine formaldehyde resin.

[0058] In some optional embodiments, the mass content of the flame retardant X in the flame retardant polymer material can be 0.1% to 10%, such as any value among 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0% and 10.0%, or any range between two values.

[0059] The following examples are given for illustrative purposes and are not intended to limit the scope of the present disclosure.Unless otherwise stated, all percentages in the following examples are by weight.

[0060] raw material:

[0061] (1) Diethylphosphinic acid chloride (including diethylphosphinic acid chloride and ethylbutylphosphinic acid chloride) and cyclic phosphate CU flame retardant were purchased from Jiangsu Liside New Materials Co., Ltd.;

[0062] (2) Methanol, n-propanol, n-butanol, 2-ethylhexanol (isooctanol), triethylamine, and N,N-dimethyl-p-toluidine were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0063] (3) Polyurethane rigid foam polyether 6305 and rigid foam silicone oil M88108 were purchased from Nanjing Meiside Chemical Co., Ltd.;

[0064] (4) The catalyst for polyurethane rigid foam was dimethylcyclohexylamine (PC-8), the blowing agent was pentafluoropropane (HFC-245FA), polymeric MDI, triethyl phosphate (TEP), dimethyl methyl phosphate (DMMP), and diethyl ethyl phosphate (DEEP) were purchased from commercial sources; dibutyl ethyl phosphate, dihexyl ethyl phosphate, and dioctyl ethyl phosphate were prepared according to the method described in the reference (An efficient method for the esterification of phosphonic and phosphoric acids using silica chloride, DOI: 10.1016 / j.tetlet.2006.02.159).

[0065] (5) In the following examples, the moisture content of the phosphate flame retardant components A and B is less than 0.3%.

[0066] test:

[0067] (1) Acid value determination:

[0068] The test was carried out using KOH ethanol solution titration method.

[0069] (2) 1H NMR, 31 P NMR test:

[0070] The test was performed using a BRUKER AVANCE 400 instrument.

[0071] (3) Test of the content of component A and component B in organophosphate:

[0072] Testing is performed by gas chromatography or liquid chromatography.

[0073] Synthesis of diethyl methyl hypophosphite:

[0074] 1) Dissolve 80.1 g of diethylphosphinoyl chloride in 200 ml of tetrahydrofuran solvent to obtain solution M;

[0075] 2) Dissolve 30.2 g of methanol and 50.5 g of triethylamine catalyst in 100 ml of tetrahydrofuran to obtain N solution;

[0076] 3) At 66°C, slowly add solution M to solution N via a dropping funnel with stirring. Monitor the reaction progress using 31P NMR. Addition is complete within approximately 1 hour. After the addition is complete, continue stirring for 2 hours to terminate the reaction. Filter to remove the amine salt, remove the solvent and triethylamine by rotary evaporation, and filter the resulting triethylamine salt again. Distill under reduced pressure to obtain diethyl methyl hypophosphite flame retardant. Its acid value is 0.09 mg KOH / g.

[0077] Synthesis of diethylpropyl hypophosphite:

[0078] 1) Dissolve 80.3 g of diethylphosphinate chloride in 200 ml of toluene solvent to obtain M solution;

[0079] 2) Dissolve 58.6 g of n-propanol and 50.2 g of triethylamine catalyst in 150 ml of toluene to obtain N solution;

[0080] 3) At 100°C, slowly add solution M to solution N via a dropping funnel with stirring. Monitor the reaction progress using 31P NMR. Addition is complete within approximately 50 minutes. After the addition is complete, continue stirring for 2 hours to terminate the reaction. Filter to remove the amine salt, remove the solvent and triethylamine by rotary evaporation, and filter the resulting triethylamine salt again. Distill under reduced pressure to obtain diethylpropyl hypophosphite flame retardant. Its acid value is 0.12 mg KOH / g.

[0081] Synthesis of diethyl octyl hypophosphite:

[0082] 1) Dissolve 80.4 g of diethylphosphinate chloride in 190 ml of toluene solvent to obtain solution M;

[0083] 2) Dissolve 119.3 g of isooctyl alcohol and 42.6 g of N,N-dimethyl-p-toluidine catalyst in 120 ml of toluene to obtain N solution;

[0084] 3) At 105°C, slowly add solution M to solution N via a dropping funnel with stirring. Monitor the reaction progress using 31P NMR. Addition is complete within approximately 2 hours. After the addition is complete, continue stirring for 3 hours to terminate the reaction. Filter to remove the amine salt, and then remove the solvent and N,N-dimethyl-p-toluidine by rotary evaporation. Filter the resulting N,N-dimethyl-p-toluidine salt again, and distill under reduced pressure to obtain diethyl octyl hypophosphite flame retardant. Its acid value is 0.16 mg KOH / g.

[0085] Synthesis of dialkyl butyl hypophosphite A:

[0086] 1) Dissolve 73.9 g of diethylphosphinate chloride and 6.3 g of ethylbutylphosphinate chloride in 200 ml of toluene to obtain an M solution;

[0087] 2) Dissolve 71.3 g of butanol and 32.9 g of N,N-dimethyl-p-toluidine catalyst in 150 ml of toluene to obtain N solution;

[0088] 3) At 105°C, slowly add solution N to solution M via a dropping funnel with stirring. Monitor the reaction progress using 31P NMR. Addition is complete within approximately 1.5 hours. After the addition is complete, continue stirring for 2 hours to terminate the reaction. Filter to remove the amine salt, remove the solvent by rotary evaporation, and filter the resulting N,N-dimethyl-p-toluidine salt again. Distill under reduced pressure to obtain dialkyl butyl hypophosphite, comprising 94.9 wt% diethyl butyl hypophosphite and 5.1 wt% ethylbutyl phosphinate. The acid value of the dialkyl hypophosphite mixture is 0.1 mg KOH / g.

[0089] Synthesis of dialkyl butyl hypophosphite B:

[0090] 1) Dissolve 73.9 g of diethylphosphinate chloride and 6.3 g of ethylbutylphosphinate chloride in 200 ml of toluene to obtain an M solution;

[0091] 2) Dissolve 71.3 g of butanol and 32.9 g of N,N-dimethyl-p-toluidine catalyst in 150 ml of toluene to obtain N solution;

[0092] 3) At 105°C, slowly add solution N to solution M via a dropping funnel with stirring. Monitor the reaction progress using 31P NMR. Complete the addition within approximately 1.5 hours. After the addition is complete, continue stirring for 2 hours to terminate the reaction. Filter to remove the amine salt, remove the solvent by rotary evaporation, and filter the resulting N,N-dimethyl-p-toluidine salt again. Distill under reduced pressure to obtain dialkyl butyl hypophosphite, comprising 94.9 wt% diethyl butyl hypophosphite, 4.7 wt% ethyl butyl phosphinate, and 3.2 wt% butyl butyl phosphinate. The acid value of the dialkyl hypophosphite mixture is 0.1 mg KOH / g.

[0093] Synthesis of dialkyl butyl hypophosphite C:

[0094] 1) Dissolve 73.9 g of diethylphosphinate chloride and 6.3 g of ethylbutylphosphinate chloride in 200 ml of toluene to obtain an M solution;

[0095] 2) Dissolve 71.3 g of butanol and 32.9 g of N,N-dimethyl-p-toluidine catalyst in 150 ml of toluene to obtain N solution;

[0096] 3) At 105°C, slowly add solution N to solution M via a dropping funnel with stirring. Monitor the reaction progress using 31P NMR. Addition is complete within approximately 1.5 hours. After the addition is complete, continue stirring for 2 hours to terminate the reaction. Filter to remove the amine salt, remove the solvent by rotary evaporation, and filter the resulting N,N-dimethyl-p-toluidine salt again. Distill under reduced pressure to obtain dialkyl butyl hypophosphite, comprising 94.9 wt% diethyl butyl hypophosphite and 0.2 wt% butyl butylphosphinate. The acid value of the dialkyl hypophosphite mixture is 0.1 mg KOH / g.

[0097] Application of halogen-free flame retardants:

[0098] The different types of component A flame retardants prepared above were mixed with component B flame retardants in a high-speed mixer for 1 minute, allowed to stand for 20 minutes, and then applied to polyurethane. The specific operation process is as follows:

[0099] Polyether 6305, rigid foam silicone oil M88108, catalyst PC-8, water, and blowing agent HFC-245FA were added to a beaker in a mass ratio of 80:1.6:3.5:1.5:25.4 and stirred at high speed for 15 seconds to produce a mixed polyether. The organic phosphate flame retardant described in the following examples and comparative examples was then added. High-speed stirring was continued for 20 seconds to uniformly mix the components. Polymeric MDI was then added to the resulting mixture and stirred again for 10 seconds. After the mixture turned white, it was poured into a mold and allowed to foam freely. After the reaction was complete, it was placed in a 70°C oven and aged for 5 hours to produce a highly efficient, environmentally friendly, flame-retardant polyurethane foam.

[0100] The compositions of the organophosphate flame retardants in Examples 1 to 8 and Comparative Examples 1 to 8 are as follows:

[0101] Example 1

[0102] 98% diethyl methyl hypophosphite + 2% ethyl dibutyl phosphate.

[0103] Example 2

[0104] 92% diethylpropyl phosphinate + 8% dibutyl methyl phosphate.

[0105] Example 3

[0106] 91% diethyl octyl phosphinate + 9% dimethyl methyl phosphate.

[0107] Example 4

[0108] 95% dialkyl butyl hypophosphite A mixture + 5% diethyl ethyl phosphate.

[0109] Example 5

[0110] 99.98% dialkyl butyl hypophosphite A mixture + 0.02% ethyl dihexyl phosphate.

[0111] Example 6

[0112] 97.8% diethylpropyl phosphinate + 2.2% dibutyl ethyl phosphate.

[0113] Example 7

[0114] 96.8% diethylpropyl phosphinate + 1.2% ethyl dibutyl phosphate + 2% cyclic phosphate CU.

[0115] Example 8

[0116] 98.8% diethylpropyl hypophosphite + 1.2% dioctyl ethyl phosphate.

[0117] Example 9

[0118] 95% dialkyl butyl hypophosphite B mixture + 5% diethyl ethyl phosphate.

[0119] Example 10

[0120] 95% dialkyl butyl phosphinate C mixture + 5% diethyl ethyl phosphate.

[0121] Comparative Example 1

[0122] 85% diethyl methyl hypophosphite + 15% ethyl dibutyl phosphate.

[0123] Comparative Example 2

[0124] 92% diethylpropyl phosphinate + 8% triethyl phosphate.

[0125] Comparative Example 3

[0126] 100% diethyl octyl phosphinate.

[0127] Comparative Example 4

[0128] 70% dialkyl butyl hypophosphite A mixture + 30% diethyl ethyl phosphate.

[0129] Comparative Example 5

[0130] 99.995% dialkyl butyl hypophosphite A mixture + 0.005% dihexyl ethyl phosphate.

[0131] Comparative Example 6

[0132] 98% diethylpropyl phosphinate + 2% cyclic phosphate CU.

[0133] Comparative Example 7

[0134] 100% Dialkyl Butyl Phosphinate A Mixture.

[0135] Comparative Example 8

[0136] 100% dihexyl ethyl phosphate.

[0137] The following Tables 1 and 2 are the compositions of polyurethane foam materials:

[0138] Table 1

[0139] Table 2

[0140] The main performance indicators of flame retardant polyurethane foam are as follows:

[0141] 1) Flame retardant stability test (oxygen index):

[0142] The prepared M1 to M18 polyurethane foams were aged in an oven at 70° C. for 48 hours and then placed at room temperature for three days. The oxygen index was then tested according to GB-T2406.2-2009 to examine changes in flame retardant stability.

[0143] 2) Storage stability (foaming after aging)

[0144] The mixed polyether was mixed with the flame retardant according to the ratios in Table 1 and Table 2, stored in an oven at 30°C for 10 days, and then mixed with polymeric MDI again and foamed to observe the foaming condition.

[0145] 3) Dimensional stability:

[0146] The prepared polyurethane foams M1 to M18 were aged in an oven at 70° C. for 48 hours and then placed at room temperature for three days. The changes in the length dimensions of the samples before and after aging were then tested according to GB-T8811-2008.

[0147] L%=(L2-L1) / L1×100%

[0148] Where L2 is the length of the sample after aging, and L1 is the length of the sample before aging.

[0149] 4) Cell uniformity

[0150] For the obtained M1-M18 polyurethane foam, cut the cross section and observe the number of abnormal cells in an area of ​​10cm×10cm under a magnifying glass. Number>3; or cell diameter If the number is greater than 5, it is considered abnormal.

[0151] Table 3 Test results of halogen-free flame retardant polyurethane performance

[0152] As can be seen from Table 3, when component A and component B are mixed in a certain proportion, the obtained organic phosphate flame retardant, when used in polyurethane, the obtained polyurethane foam shows excellent flame retardant properties, flame retardant stability and storage stability. The dimensional change rate of the polyurethane foam after foaming is low (<1%), which can be seen from M1 to M10. The type and amount of component A and component B are also very important. In Comparative Examples 1 and 4, the proportion of component A and component B is changed, and the foaming time of the organic phosphate flame retardant during use becomes shorter, affecting its use; the thermal dimensional stability of the obtained polyurethane foam becomes worse, and the flame retardant performance of the polyurethane foam decreases seriously after aging (the oxygen index decreases by 0.5); in Comparative Example 2, the type of component B is changed, and the foaming time of the organic phosphate flame retardant during use becomes shorter, and even a burnt core appears in the foam; in Comparative Example 6, the type of component B is also changed, and the organic phosphate flame retardant is not as good as the organic phosphate flame retardant. When the phosphate flame retardant is foamed in polyurethane, the uniformity of the foam cells decreases. After adding part of component B to component A (Example 3, Comparative Example 3, Example 4, and Comparative Example 7), the flame retardant efficiency of the resulting organophosphate composition is improved, and the uniformity of the foam cells of the resulting polyurethane foam is improved. In Comparative Example 5, the amount of component B is reduced, and the uniformity of the foam cells of the resulting polyurethane foam decreases. In Comparative Example 8, component B is directly used as a flame retardant, and the flame retardant stability and storage stability of the resulting polyurethane foam are greatly reduced, and the foam size also changes significantly. Industrial Applicability

[0153] When used in polyurethane foaming, the organophosphate flame retardant provided by this disclosure can impart good storage stability to the polyether raw material of the polyurethane, and can also impart good flame retardant stability and dimensional stability to the polyurethane material. Furthermore, the organophosphate flame retardant provided by this disclosure can also be used in polymer matrix materials such as unsaturated polyesters, epoxy resins, polycarbonates, polyesters, polyphenylene ethers, polyvinyl chloride, and polyacrylic acids, providing flame retardant and fireproofing effects.

Claims

1. An organic phosphate flame retardant, characterized in that: The organic phosphate flame retardant comprises component A and component B, wherein component A is selected from at least one of the compounds represented by formula (I), and component B is selected from at least one of the compounds represented by formula (II): In formula (I), R1 and R2 are C1-C6 alkyl groups, and R3 is C1-C8 alkyl groups; In formula (II), R4 is a methyl group or an ethyl group, and R5 and R6 are C1-C8 alkyl groups.

2. The organic phosphate flame retardant according to claim 1, characterized in that In formula (I), R1 and R2 are each independently selected from a linear or branched C1 to C6 alkyl group, R1 and R2 may be the same or different, and R3 is selected from a linear or branched C1 to C8 alkyl group; in formula (II), R4 is methyl or ethyl, R5 and R6 are each independently selected from a linear or branched C1 to C8 alkyl group, R5 and R6 may be the same or different.

3. The organic phosphate flame retardant according to claim 1 or 2, characterized in that The weight proportions of component A and component B in the organic phosphate flame retardant in the composition are respectively: component A: 90.0 wt% to 99.99 wt%, component B: 0.01 wt% to 10.0 wt%.

4. The organic phosphate flame retardant according to any one of claims 1 to 3, characterized in that By weight percentage, the water content of component A is less than 0.3%; the water content of component B is less than 0.3%.

5. The organic phosphate flame retardant according to any one of claims 1 to 4, characterized in that Calculated by weight percentage, the moisture content in the organic phosphate flame retardant is less than 0.3%.

6. A method for preparing the organophosphate flame retardant according to any one of claims 1 to 5, characterized in that: include: Component A is synthesized with dialkyl hypophosphite chloride and alkyl alcohol as raw materials, and then component A and component B are mixed to obtain an organic phosphate flame retardant.

7. The preparation method according to claim 6, characterized in that The preparation method of the component A is as follows: dialkyl hypophosphite chloride and alkyl alcohol are synthesized at 40° C. to 200° C.

8. The preparation method according to claim 7, characterized in that The synthesis temperature is 40°C to 150°C.

9. A flame retardant polymer material, characterized in that: The flame retardant comprises a polymer matrix material and the organic phosphate flame retardant according to any one of claims 1 to 5.

10. The flame retardant polymer material according to claim 9, characterized in that: The polymer matrix material includes at least one of polyurethane, unsaturated polyester resin, epoxy resin, polycarbonate, polyester, polyphenylene ether, polyvinyl chloride and polyacrylic acid.

11. The flame retardant polymer material according to claim 10, characterized in that: The polymer matrix material is selected from polyurethane, epoxy resin or unsaturated polyester resin.

12. The flame-retardant polymer material according to any one of claims 9 to 11, wherein the weight proportions of the organic phosphate flame retardant and the polymer matrix material in the flame-retardant polymer material are: organic phosphate flame retardant: 5wt% to 40wt%, polymer matrix material: 60wt% to 95wt% respectively.

13. The flame retardant polymer material according to any one of claims 9 to 12, characterized in that: The flame retardant polymer material further includes one or more functional additives and flame retardant X.

14. The flame retardant polymer material according to claim 13, characterized in that: The functional additives include at least one of a reinforcing agent, an anti-dripping agent, a stabilizer, a pigment, a carbon-forming catalyst, a dispersant, a nucleating agent, an inorganic filler, an organic filler, an antioxidant and an antibacterial agent, and the mass content of the functional additives in the flame retardant polymer material is 5% to 40%.

15. The flame retardant polymer material according to claim 13 or 14, characterized in that: The flame retardant X is selected from at least one of a phosphorus-based flame retardant and a nitrogen-based flame retardant, and the mass content of the flame retardant X in the flame-retardant polymer material is 0.1% to 10%.

16. The flame retardant polymer material according to claim 15, characterized in that: The phosphorus-based flame retardant includes at least one of a phosphate ester and a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative.

17. The flame retardant polymer material according to claim 15, characterized in that: The nitrogen-based flame retardant includes at least one of melamine cyanurate, melamine polyphosphate and etherified melamine formaldehyde resin.

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