CN111620999A - Heat-conducting and insulating halogen-free flame-retardant polyurethane - Google Patents
Heat-conducting and insulating halogen-free flame-retardant polyurethane Download PDFInfo
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- C08K5/51—Phosphorus bound to oxygen
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Abstract
The invention belongs to the technical field of polyurethane, and particularly relates to heat-conducting and insulating halogen-free flame retardant polyurethane. The invention provides a guideThe thermal insulation halogen-free flame retardant polyurethane comprises, by weight, 19-23 parts of polyisocyanate, 34-38 parts of polyol, 0.8-1.2 parts of antioxidant, 13-17 parts of filler and 18-22 parts of alkyl phosphinate. The polyurethane described herein has excellent insulating properties (insulation resistance greater than 10)12Omega cm), flame retardant properties and heat conducting properties, and is halogen-free; the isocyanate, the polyol and the chain extender generate a polyurethane material, the flame retardant effect of the polyurethane obtained by adding the alkyl hypophosphite reaches UL94-V0, and the aluminum oxide and the silicon nitride are uniformly dispersed in the polyurethane, so that the hardness and the heat conductivity of the polyurethane are improved.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to heat-conducting and insulating halogen-free flame retardant polyurethane.
Background
The polyurethane is a high molecular compound and is named polyurethane. The polyurethane has excellent mechanical properties and good chemical reagent resistance, acid and alkali resistance, weather resistance, water resistance, high adhesion and other properties, so that the polyurethane can be widely applied to cables, thin film sheets, conveyer belts, injection molding products and the like. With the ever-expanding range of applications, it is becoming increasingly recognized that it is of paramount importance to improve the flame retardancy of polyurethane materials. Therefore, the development and application of flame-retardant polyurethane materials have become important issues in the field of polyurethane materials. The polyurethane material is flame-retardant, and the specific main method comprises the following steps: (1) introducing a reactive flame retardant; that is, elements with flame retardant effect, such as phosphorus, halogen and the like, are introduced into the raw materials of the polyurethane material; (2) adding additive flame retardant, specifically adding a substance which has no reactivity but has flame retardant effect into the raw materials. CN103524698A adopts diethyl hypophosphite and bis (2-hydroxyethyl) aminomethylene diethyl phosphate as flame retardants to prepare a polyurethane pouring sealant, the flame retardant property of the composite material is UL-94V0 grade, but the thermal conductivity is only 0.63W/(mK).
Flame retardant specifications are becoming increasingly stringent for many applications, and polyurethanes that are thermally conductive, insulative, and halogen-free have become the focus of research.
Disclosure of Invention
In order to solve the technical problem, the invention provides heat-conducting and insulating halogen-free flame retardant polyurethane which comprises, by weight, 19-23 parts of polyisocyanate, 34-38 parts of polyol, 0.8-1.2 parts of antioxidant, 13-17 parts of filler and 18-22 parts of alkyl phosphinate.
As a preferable technical scheme, the heat-conducting and insulating halogen-free flame retardant polyurethane comprises, by weight, 20.88 parts of polyisocyanate, 36.32 parts of polyol, 1 part of antioxidant, 15.5 parts of filler and 20 parts of alkyl phosphinate.
As a preferable technical scheme, the polyisocyanate is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
As a preferred technical scheme, the polyol is polyether polyol and/or polyester polyol.
As a preferable technical scheme, the antioxidant is at least one selected from the antioxidant 1010, the antioxidant 405, the antioxidant 168, the antioxidant DNP, the antioxidant DLTP, the antioxidant CA and the antioxidant 1076.
In a preferred embodiment, the filler is at least one selected from the group consisting of aluminum nitride, silicon nitride, silica, alumina, and bentonite.
As a preferable technical scheme, the weight ratio of the aluminum nitride to the silicon nitride is (4.5-6): 1.
as a preferable technical scheme, the components also comprise 4-8 parts of chain extender, 0.1-0.5 part of wax and 0-0.2 part of coupling agent by weight.
The second aspect of the invention provides a preparation method of the halogen-free flame retardant polyurethane, which comprises the following steps: (1) firstly, dehydrating polyisocyanate and polyol in vacuum; (2) adding an antioxidant, a filler and alkyl phosphinate into the mixture obtained in the step (1) and uniformly mixing; (3) and (3) adding the mixture obtained in the step (2) into a high-speed stirring and mixing head, pouring the mixture into a block material, and placing the block material in a drying room at the temperature of 110-.
The third aspect of the invention provides the application of the halogen-free flame retardant polyurethane in cables, film sheets, conveyer belts and injection molding products.
Has the advantages that: the polyurethane described herein has excellent insulating properties (insulation resistance greater than 10)12Omega cm), flame retardant properties and heat conducting properties, and is halogen-free; the isocyanate, the polyol,The chain extender generates a polyurethane material, the flame retardant effect of the polyurethane obtained by adding the alkyl hypophosphite reaches UL94-V0, and the aluminum oxide and the silicon nitride are uniformly dispersed in the polyurethane, so that the hardness and the heat conductivity of the polyurethane are improved.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
In order to solve the problems, the invention provides heat-conducting and insulating halogen-free flame retardant polyurethane which comprises, by weight, 19-23 parts of polyisocyanate, 34-38 parts of polyol, 0.8-1.2 parts of antioxidant, 13-17 parts of filler and 18-22 parts of alkyl phosphinate.
Preferably, the heat-conducting and insulating halogen-free flame retardant polyurethane comprises, by weight, 20.88 parts of polyisocyanate, 36.32 parts of polyol, 1 part of antioxidant, 15.5 parts of filler and 20 parts of alkyl phosphinate.
In a preferred embodiment, the polyisocyanate is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
As a preferred embodiment, the polyol is a polyether polyol and/or a polyester polyol; preferably, the polyol is polyester polyol, and the average molecular weight is 800-5000; the aliphatic polyester polyol polyurethane contains more ester groups, amino groups and other polar groups in molecules, and has strong cohesive strength and adhesive force, high strength and wear resistance; the polyurethanes made from the aromatic polyesters have excellent hydrolysis resistance, heat resistance and adhesion. More preferably, the polyol is an adipic acid-based polyester polyol; further preferably, the polyol is PBA 1000.
In a preferred embodiment, the antioxidant is at least one selected from the group consisting of antioxidant 1010, antioxidant 405, antioxidant 168, antioxidant DNP, antioxidant DLTP, antioxidant CA, and antioxidant 1076. The chemical name of the antioxidant 1010 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, the antioxidant is white crystalline powder, and the chemical property is stable.
As a preferred embodiment, the filler is selected from at least one of aluminum nitride, silicon nitride, silica, alumina, bentonite; preferably, the filler is aluminum nitride or silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is (4.5-6): 1; more preferably, the weight ratio of the aluminum nitride to the silicon nitride is 5.2: 1.
the alkyl phosphinate contains P-C bonds, P-O bonds and P ═ O bonds, so that on one hand, the flame retardant property of the phosphorus flame retardant is fully exerted due to the high content of P, and the flame retardant effect can be realized in a condensed phase and a gas phase at the same time; PO is formed in a gas phase during thermal decomposition, high-energy free radicals can be captured to produce stable HPO and PO, and chain reaction of the free radicals is inhibited; in the condensed phase, the condensed phase reacts with oxygen at high temperature, is heated and gradually decomposed into a viscous liquid film of phosphate, covers the surface of the burner and isolates air. On the other hand, the existence of the metal cation can prevent the volatilization loss of the flame retardant and the environmental pollution, and simultaneously, the salt of the metal cation has good smoke suppression effect.
As a preferred embodiment, the alkyl phosphinate is selected from at least one of aluminum diethylphosphinate, aluminum phosphinate, melamine polyphosphate, methylphenyl phosphinate, and hydroxymethylphenyl phosphinate.
The molecular formula of the diethyl aluminum phosphinate is Al (PO)2C4H10)3CAS number 225789-38-8. The aluminum diethylphosphinate can play a role in a condensed phase to promote polymer carbon formation and can remove high-energy free radicals in a combustion zone.
As a preferred embodiment, the component further comprises 4-8 parts of chain extender, 0.1-0.5 part of wax and 0-0.2 part of coupling agent, wherein the coupling agent is not 0.
As a preferred embodiment, the chain extender is a small molecule alcohol and/or amine substance; preferably, the chain extender is a small molecular alcohol; more preferably, the chain extender is a dihydric alcohol with the carbon atom number of 2-6; further preferably, the chain extender is 1, 4-butanediol.
The wax is a mixture of several higher alkanes, mainly n-docosane (C)22H46) And n-octacosane (C)28H58) About 85% carbon containing elements and about 14% hydrogen containing elements; preferably, the wax is selected from at least one of petroleum wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate copolymer wax, oxidized polyethylene wax and modified polyethylene wax; more preferably, the wax is a polytetrafluoroethylene-modified polyethylene wax; the polytetrafluoroethylene modified polyethylene wax is a commercial product, is not particularly limited, and is preferably BYK-CERAFLOUR-996.
The coupling agent is a silane coupling agent having a molecular formula generally Y-R-Si (OR)3Thus, when a silane coupling agent is interposed between the inorganic and organic interfaces, an organic substrate-silane coupling agent-inorganic substrate bonding layer can be formed, the silane coupling agent is a commercially available product without particular limitation, and preferably, the silane coupling agent includes at least one of 3-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β -methoxyethoxy) silane, and further, the coupling agent is KBE-903, which is a Japanese trademark.
The polyurethane described herein has excellent insulating properties (insulation resistance greater than 10)12Omega cm), flame retardant properties and heat conducting properties, and is halogen-free; the isocyanate, the polyol and the chain extender generate a polyurethane material, the flame retardant effect of the polyurethane obtained by adding the alkyl hypophosphite can reach UL94-V0, the aluminum oxide and the silicon nitride are uniformly dispersed in the polyurethane, the hardness and the heat conductivity of the polyurethane are improved, particularly, the alkyl hypophosphite is diethyl aluminum phosphinate, the coupling agent KBE-903 and the modified polyethylene wax with the model number of BYK-CERAFLOUR-996 are added, and the proportion of the two is 1: (2-4), the formation of large-area heat conduction channels in the polyurethane by the aluminum oxide and the silicon nitride is promoted, so that the heat conduction channels are formed in large areas in the polyurethaneThe thermal conductivity of the obtained polyurethane is more than 2W/(m.K).
A second aspect of the present application provides a method for preparing the polyurethane material, comprising the steps of: (1) firstly, dehydrating polyisocyanate and polyol in vacuum; (2) adding an antioxidant, a filler and alkyl phosphinate into the mixture obtained in the step (1) and uniformly mixing; (3) and (3) adding the mixture obtained in the step (2) into a high-speed stirring and mixing head, pouring the mixture into a block material, and placing the block material in a drying room at the temperature of 110-.
Preferably, the preparation method of the polyurethane material comprises the following steps: (1) firstly, dehydrating polyisocyanate, polyol and a chain extender in vacuum; (2) adding an antioxidant, a filler, alkyl phosphinate, wax and a coupling agent into the mixture obtained in the step (1) and uniformly mixing; (3) and (3) adding the mixture obtained in the step (2) into a high-speed stirring and mixing head, pouring the mixture into a block material, and placing the block material in a drying room at the temperature of 110-.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
The halogen-free flame retardant polyurethane with excellent insulating and flame retardant properties comprises, by weight, 19 parts of diphenylmethane diisocyanate, 100034 parts of PBA, 10100.8 parts of an antioxidant, 13 parts of a filler, 18 parts of aluminum diethylphosphinate, 4 parts of 1, 4-butanediol, 0.1 part of wax and 0.05 part of a coupling agent.
The filler is aluminum nitride and silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is 4.5: 1. the wax is BYK-CERAFLOUR-996, and the coupling agent is KBE-903.
The preparation method of the halogen-free flame retardant polyurethane comprises the following steps of (1) firstly, carrying out vacuum dehydration on diphenylmethane diisocyanate and PBA1000, 1, 4-butanediol; (2) adding an antioxidant, a filler, alkyl phosphinate, wax and a coupling agent into the mixture obtained in the step (1) and uniformly mixing; (3) and (3) adding the mixture obtained in the step (2) into a high-speed stirring mixing head, pouring the mixture into a block material, and placing the block material in a drying room for 2 hours at 120 ℃ to obtain the material.
Example 2
The halogen-free flame retardant polyurethane with excellent insulating and flame retardant properties comprises, by weight, 20.88 parts of diphenylmethane diisocyanate, 100036.32 parts of PBA, 10101 parts of an antioxidant, 15.5 parts of a filler, 20 parts of aluminum diethylphosphinate, 5.9 parts of 1, 4-butanediol, 0.3 part of wax and 0.1 part of a coupling agent.
The filler is aluminum nitride and silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is 5.2: 1. the wax is BYK-CERAFLOUR-996, and the coupling agent is KBE-903.
The specific steps of the preparation method of the halogen-free flame retardant polyurethane are the same as example 1.
Comparative example 1
The halogen-free flame retardant polyurethane with excellent insulating and flame retardant properties comprises, by weight, 20.88 parts of diphenylmethane diisocyanate, 100036.32 parts of PBA, 10101 parts of an antioxidant, 15.5 parts of a filler, 20 parts of aluminum hypophosphite, 5.9 parts of 1, 4-butanediol, 0.3 part of wax and 0.1 part of a coupling agent.
The filler is aluminum nitride and silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is 5.2: 1. the wax is BYK-CERAFLOUR-996, and the coupling agent is KBE-903.
The specific steps of the preparation method of the halogen-free flame retardant polyurethane are the same as example 1.
Comparative example 2
The halogen-free flame retardant polyurethane with excellent insulating and flame retardant properties comprises, by weight, 20.88 parts of diphenylmethane diisocyanate, 100036.32 parts of PBA, 10101 parts of an antioxidant, 15.5 parts of a filler, 20 parts of aluminum diethylphosphinate, 5.9 parts of 1, 4-butanediol, 0.3 part of wax and 0.1 part of a coupling agent.
The filler is aluminum nitride and silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is 5.2: 1. the wax is BYK-CERAFLOUR-996, and the coupling agent is a vinyl triethoxysilane coupling agent.
The specific steps of the preparation method of the halogen-free flame retardant polyurethane are the same as example 1.
Comparative example 3
The halogen-free flame retardant polyurethane with excellent insulating and flame retardant properties comprises, by weight, 20.88 parts of diphenylmethane diisocyanate, 100036.32 parts of PBA, 10101 parts of an antioxidant, 15.5 parts of a filler, 20 parts of aluminum diethylphosphinate, 5.9 parts of 1, 4-butanediol, 0.3 part of wax and 0.01 part of a coupling agent.
The filler is aluminum nitride and silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is 5.2: 1. the wax is BYK-CERAFLOUR-996, and the coupling agent is KBE-903.
The specific steps of the preparation method of the halogen-free flame retardant polyurethane are the same as example 1.
Comparative example 4
The halogen-free flame retardant polyurethane with excellent insulating and flame retardant properties comprises, by weight, 20.88 parts of diphenylmethane diisocyanate, 100036.32 parts of PBA, 10101 parts of an antioxidant, 15.5 parts of a filler, 20 parts of aluminum diethylphosphinate, 5.9 parts of 1, 4-butanediol, 0.3 part of wax and 1 part of a coupling agent.
The filler is aluminum nitride and silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is 5.2: 1. the wax is BYK-CERAFLOUR-996, and the coupling agent is KBE-903.
The specific steps of the preparation method of the halogen-free flame retardant polyurethane are the same as example 1.
Comparative example 5
The halogen-free flame retardant polyurethane with excellent insulating and flame retardant properties comprises, by weight, 20.88 parts of diphenylmethane diisocyanate, 100036.32 parts of PBA, 10101 parts of an antioxidant, 15.5 parts of a filler, 20 parts of aluminum diethylphosphinate, 5.9 parts of 1, 4-butanediol, 0.3 part of wax and 1 part of a coupling agent.
The filler is aluminum nitride and silicon nitride; the weight ratio of the aluminum nitride to the silicon nitride is 5.2: 1. the wax is polyethylene wax, and the type of the coupling agent is KBE-903.
The specific steps of the preparation method of the halogen-free flame retardant polyurethane are the same as example 1.
Performance testing
(1) The polyurethanes described in examples 1-2 were tested for properties and the results are shown in Table 1.
TABLE 1
| Test items | Test standard | Test data |
| Tensile strength | ISO527 | 28-30Mpa |
| Elongation (Elongation) | ISO527 | 550-560％ |
| Flame-retardant effect | UL-94 | UL94-V0 |
| Coefficient of thermal conductivity | GB1029 | 2.26-2.5W/(m·k) |
(2) The thermal conductivity and flame retardant effect of the polyurethane described in comparative example are shown in table 2.
TABLE 2
| Thermal conductivity W/(m.k) | Flame-retardant effect | |
| Comparative example 1 | 1.67 | V0 |
| Comparative example 2 | 1.35 | V1 |
| Comparative example 3 | 0.85 | V1 |
| Comparative example 4 | 1.85 | V0 |
| Comparative example 5 | 154 | V1 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content disclosed above into an equivalent embodiment with equivalent changes, but all those simple modifications, equivalent changes and modifications made on the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The heat-conducting and insulating halogen-free flame-retardant polyurethane is characterized by comprising, by weight, 19-23 parts of polyisocyanate, 34-38 parts of polyol, 0.8-1.2 parts of antioxidant, 13-17 parts of filler and 18-22 parts of alkyl phosphinate.
2. The halogen-free flame retardant polyurethane of claim 1 comprising, by weight, 20.88 parts of polyisocyanate, 36.32 parts of polyol, 1 part of antioxidant, 15.5 parts of filler, and 20 parts of alkyl phosphinate.
3. The halogen-free flame retardant polyurethane of claim 1 or 2 wherein the polyisocyanate is selected from at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.
4. The halogen-free flame retardant polyurethane of claim 1 wherein the polyol is a polyether polyol and/or a polyester polyol.
5. The halogen-free flame retardant polyurethane of claim 1 wherein the antioxidant is at least one selected from the group consisting of antioxidant 1010, antioxidant 405, antioxidant 168, antioxidant DNP, antioxidant DLTP, antioxidant CA, and antioxidant 1076.
6. The halogen-free flame retardant polyurethane of claim 1 wherein the filler is selected from at least one of aluminum nitride, silicon nitride, silica, alumina, bentonite.
7. The halogen-free flame retardant polyurethane of claim 6 wherein the weight ratio of aluminum nitride to silicon nitride is (4.5-6): 1.
8. the halogen-free flame retardant polyurethane of any of claims 1-7 wherein the components further comprise, by weight, 4-8 parts of a chain extender, 0.1-0.5 part of a wax, and 0-0.2 part of a coupling agent.
9. A process for the preparation of a halogen-free flame retardant polyurethane according to any of claims 1 to 8 comprising the steps of: (1) firstly, dehydrating polyisocyanate and polyol in vacuum; (2) adding an antioxidant, a filler and alkyl phosphinate into the mixture obtained in the step (1) and uniformly mixing; (3) and (3) adding the mixture obtained in the step (2) into a high-speed stirring and mixing head, pouring the mixture into a block material, and placing the block material in a drying room at the temperature of 110-.
10. Use of the halogen-free flame retardant polyurethane according to any of claims 1 to 9 in cables, film sheets, conveyor belts, injection molded products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010523089.5A CN111620999A (en) | 2020-06-10 | 2020-06-10 | Heat-conducting and insulating halogen-free flame-retardant polyurethane |
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114539764A (en) * | 2021-04-19 | 2022-05-27 | 东莞市英捷工程塑料有限公司 | Low-hardness flame-retardant high polymer material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539764A (en) * | 2021-04-19 | 2022-05-27 | 东莞市英捷工程塑料有限公司 | Low-hardness flame-retardant high polymer material and preparation method thereof |
| CN114539764B (en) * | 2021-04-19 | 2024-04-02 | 东莞市英捷工程塑料有限公司 | Flame-retardant high polymer material with low hardness and preparation method thereof |
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