CN121219302A - Flame-retardant polyurethane and its applications - Google Patents
Flame-retardant polyurethane and its applicationsInfo
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- CN121219302A CN121219302A CN202480034487.7A CN202480034487A CN121219302A CN 121219302 A CN121219302 A CN 121219302A CN 202480034487 A CN202480034487 A CN 202480034487A CN 121219302 A CN121219302 A CN 121219302A
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- 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
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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Abstract
A flame retardant polyurethane obtained by reacting a polyol and an isocyanate in the presence of a flame retardant comprising a phosphinate of formula (I) wherein R1 is a hydrocarbyl group selected from C 1-C12 alkyl and C 6-C20 aryl, and wherein R2 and R3, identical or different, independently represent H or C 1-C12 alkyl.
Description
Technical Field
The present invention relates to flame retardant polyurethanes containing a specific type of phosphinate flame retardant, a process for their manufacture and their use in industry.
Background
Flame retardant modified polyurethanes are often combined with at least one type of flame retardant substance in order to achieve the flame retardancy required for industrial use. In these applications, liquid flame retardants are often preferred over their solid counterparts. This preference derives from the several advantageous properties that liquid flame retardants can be more easily and uniformly dispersed or even dissolved within the polymer during blending than solid flame retardants, thereby providing an overall consistent flame retardant effect. In addition, liquid flame retardants can often be processed at lower temperatures than solids, alleviating the potential polymer degradation problems associated with higher temperatures. Due to their larger surface area for interaction, these liquid additives can be incorporated into the resin mixture faster than solids. In addition, liquid flame retardants can generally be more easily handled during blending with polyols, allowing precise dosage control and seamless integration with polymer formulations.
One popular liquid flame retardant widely used in the industry is TCPP (tris (1-chloro-2-propyl) phosphate), which is often incorporated into polyurethane foams in consumer and household insulation and electronics. However, while providing effective flame retardancy, TCPP was found to escape over time into the environment, causing negative toxicological and ecotoxicological effects due to its halogenated nature. Furthermore, leaching of the TCPP flame retardant results in a decrease in overall flame retardant effectiveness over time.
US 9 631 144 B2 describes a different liquid flame retardant composition comprising one or more halogenated flame retardants which are brominated epoxides obtained by reacting tetrabromobisphenol a with epichlorohydrin. This particular liquid flame retardant is said to provide stable incorporation in rigid polyurethane foams and to exhibit good flame retardancy. However, it is notable that in the working examples provided in US 9 631 144 B2, the brominated epoxide is obtained in the form of a resin having a high softening point, so that further processing at high temperatures is necessary. Furthermore, the resulting liquid flame retardant composition is characterized by a high bromine content of at least 30 wt. -%, among other things.
In view of the growing concern over the use of halogenated flame retardants due to environmental protection, efforts have been made to find alternative halogen-free liquid flame retardants for polymers and polymer foams.
US 4 458 035A describes oligomeric phosphate flame retardants for polyurethane foams and the phosphate esters have the formula (1) below, wherein
N is a number from 0 to 10,
R is C 1-C10 (halo) alkyl and
R 1 and R 2 are a hydrogen atom or a C 1-C10 (halo) alkyl group.
US 7,288,577 B1 describes a blend of two different phosphate flame retardants for polyurethanes consisting essentially of:
(a) 50% by weight of the blend of butylated triphenyl phosphate, and
(B) 50% by weight of the blend of poly (ethylidenyloxy) phosphate.
Although the above-mentioned patent publications may have mentioned some effective liquid phosphorus-based flame retardants, it has been found that some of them are prone to hydrolysis under humid conditions, which in turn leads to an adverse effect on the polymerization process or the final polymer properties. In particular, it is known that the acid formed by hydrolysis may deactivate the polymerization catalyst during the foaming process and further cleave covalent bonds in the polymer foam product, thereby disrupting the desired 3-D foam network.
Several liquid phosphorus-based flame retardant products are commercially available, including anti-blaze 1045 (available from Albemarle), a cyclic phosphonate compound commonly used in polymers such as PET and PBT. The chemical structure of this cyclic phosphonate is shown by the following formula (2).
The anti-blaze 1045 has a high viscosity, typically 500,000 mPas or more at a temperature of 25 ℃. Thus, its effective use may involve careful impregnation onto the support material or careful application as an aqueous solution to the surface of the polymer fibres. In the latter case, subsequent heating is required to achieve softening of the fiber and dissolution of the cyclic phosphonate to achieve the desired result.
Disclosure of Invention
Summary of The Invention
The object of the present invention is to provide a novel halogen-free flame retardant for polyurethanes, in particular polyurethane foams. The halogen-free flame retardant is in liquid form at room temperature and under conventional polyurethane manufacturing conditions, has a suitably low viscosity for ease of processing and handling, exhibits excellent hydrolytic stability even under humid conditions, and provides an equivalent or enhanced level of flame retardancy to polyurethane materials as compared to existing commercial standards.
The present invention aims to provide a flame retardant polyurethane, particularly a polyurethane foam, which achieves superior flame retardant efficiency by integrating the above halogen-free flame retardant.
The invention provides the use of phosphinates of the formula (I) as flame retardants for polyurethanes
Wherein R1 is a hydrocarbyl group selected from the group consisting of C 1-C12 alkyl and C 6-C20 aryl;
And wherein R2 and R3, which are the same or different, independently represent H or C 1-C12 alkyl.
The invention further provides flame retardant polyurethanes obtained by reacting a polyol and an isocyanate in the presence of a flame retardant comprising a phosphinate of formula (I).
Detailed Description
The term "hydrocarbyl" as used herein, unless otherwise indicated, refers to an aliphatic, aromatic, or cycloaliphatic radical, which may be saturated or unsaturated, straight-chain or branched, and which is optionally substituted with heteroatoms such as O, N, S.
Preferably, R1 is selected from C1-C6 alkyl, more preferably from C2-C4 alkyl.
Also preferably, R2 and R3 are not both H.
In a preferred embodiment of the invention, one of R2 and R3 is H or ethyl and the other is C1-C6 alkyl.
In another preferred embodiment of the invention, one of R2 and R3 is methyl and the other is H or C1-C4 alkyl.
In a particularly preferred embodiment, R1 is ethyl, one of R2 and R3 is methyl and the other is ethyl.
In another particularly preferred embodiment, R1 is butyl, one of R2 and R3 is methyl and the other is H.
In yet another particularly preferred embodiment, R1 is butyl, one of R2 and R3 is methyl and the other is butyl.
The phosphinate flame retardant according to the invention, due to its chemical nature, takes on a liquid form at room temperature and under conventional polyurethane manufacturing conditions. Advantageously, the liquid form of the phosphinate flame retardant is further characterized by a low viscosity of less than 100 mPa s, preferably less than 50 mPa s, more preferably less than 10 mPa s at a temperature of 25 ℃. The viscosity can be measured by DIN 51398. As mentioned above, the advantageous properties of low viscosity may play an important role in the practical application of liquid flame retardants for the manufacture of flame retardant polyurethanes. The use of viscous liquid flame retardants presents challenges because they typically require heating of the containers, feed lines, and discharge lines involved in the storage or transportation of the liquid. Furthermore, the uniform incorporation of highly viscous flame retardant liquids into polymer compositions often requires additional effort, especially in large scale industrial processes for high volume chemical production.
The phosphinates of the formula (I) can be prepared by different processes. One option is to react an alpha-monoolefin with an (alkyl) phosphinate in the presence of a free radical generator as described in U.S. Pat. No. 4,345A, EP 23,666 A1, U.S. Pat. No. 87,477 B2 and EP 23,67,834 A1.
The phosphinates of the formula (I) can also be prepared from their corresponding phosphites by catalytic rearrangement. For example, one corresponding phosphite has the following structure (II):
This preparation can be achieved by a two-step process, as exemplified in synthetic example 1. In the first step, one of the corresponding phosphites of the desired phosphinate product is produced as intermediate product, while in the second step, this intermediate product is subjected to a catalytic rearrangement reaction to obtain the phosphinate of formula (I). Or if the corresponding phosphite is readily available in the chemical market, the preparation process may be simplified to a one-step reaction.
The rearrangement catalyst in this preparation process may be an iodine-containing catalyst and a lewis acid catalyst, such as iodine, alkyl iodides and alkali metal iodide salts (especially potassium iodide), such as those described in CN 104693238 a. Alternatively, the rearrangement catalyst may be sodium iodide as described in CN 109400643 a.
Advantageously, the rearrangement catalyst may be a small organic molecule sulfonate, more advantageously selected from diethyl sulfate, ethyl ethane sulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-chlorobenzenesulfonate and ethyl p-chlorobenzenesulfonate. Benefits of using small organic molecule sulfonate rearrangement catalysts in such a preparation process include cost effectiveness and simplified catalyst recovery, among others.
When R2 or R3 is H, the phosphinates of formula (I) can be prepared as exemplified in synthesis example 2 by reacting an alkyl dichlorophosphine with an alcohol at moderate temperature. This reaction, known as alcoholysis, is known to result in partial oxidation of the phosphine to form the corresponding alkyl phosphinate, with the production of a P-H bond.
An illustrative example of this chemistry is given in CN 113493478a, where methyl dichlorophosphine is reacted with n-butanol at room temperature. The reaction produces n-butyl methyl phosphinate as the desired product with the formation of hydrogen chloride and n-butyl chloride as by-products.
The present invention also provides a flame retardant polymer obtained by reacting monomers under polymerization conditions in the presence of a flame retardant comprising a phosphinate of formula (I).
The flame retardant Polyurethane (PUR) of the present invention is a polyurethane composition comprising a phosphinate of formula (I) as flame retardant. In one embodiment of the polyurethane composition, the phosphinate of formula (I) is present in an amount of 0.5 wt.% to 30 wt.%, relative to the weight of the polyurethane. Preferably, the phosphinate of formula (I) is present in an amount of from 0.5 wt.% to 20 wt.%, relative to the weight of the polyurethane.
The flame retardant polyurethane of the invention is preferably obtained by reacting a polyol and an isocyanate in the presence of a flame retardant comprising a phosphinate of formula (I), optionally in the presence of a polymerization catalyst. Suitable polymerization catalysts for producing flame retardant polyurethanes may be selected from aliphatic tertiary amines (e.g. triethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (e.g. 1, 4-diaza (2, 2) bicyclooctane), aliphatic amino ethers (e.g. dimethylaminoethyl ether and N, N, N-trimethyl-N-hydroxyethyl-diaminoethyl ether), cycloaliphatic amino ethers (e.g. N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, ureas, urea derivatives (e.g. aminoalkylureas, see e.g. EP-A0 176 013, in particular (3-dimethylaminopropylamine) urea) and tin catalysts (e.g. dibutyltin oxide, dibutyltin dilaurate, tin octoate).
One significant advantage of using the phosphinates of formula (I) as flame retardants for polyurethanes is their high compatibility with polyols, a necessary starting material for polyurethanes. The phosphinates of formula (I) can be readily dissolved in the polyol to form homogeneous solutions which remain stable for extended periods of time during storage or transport. Such a homogeneous solution serves as a beneficial starting material for the polymerization, thereby ensuring that the resulting polyurethane product has an overall uniformly distributed flame retardancy.
The present invention provides a method of making a flame retardant polyurethane comprising preparing a mixture comprising a polyol and a flame retardant comprising a phosphinate of formula (I), and adding an isocyanate compound to the mixture.
For the purposes of the present invention, the term "polyol" refers to a compound having at least two hydrogen atoms capable of reacting with isocyanate. These are compounds having an amino group, a thio group or a carboxyl group, preferably compounds having a hydroxyl group, in particular 2 to 8 hydroxyl groups.
Suitable polyols for the purposes of the present invention include those having a molecular weight (Mw) of 400 to 10,000, in particular those having a molecular weight of 1000 to 6000, preferably 2000 to 6000, and generally dihydroxy to octahydroxy, preferably dihydroxy to hexahydroxy polyethers or polyesters or polycarbonates or polyesteramides, as are known per se for the production of homogeneous or cellular polyurethanes, and as described, for example, in DE-A28 32 253.
Preferred polyester polyols are obtained by polycondensation of polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, methylpentanediol, 1, 6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, glucose and/or sorbitol with dibasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid and/or terephthalic acid. These polyester polyols may be used alone or in combination.
For the production of thermoset flame retardant polyurethanes, another group of preferred polyester polyols are those having two, three or four hydroxyl groups, including ethylene glycol, propylene glycol, trimethylolpropane and pentaerythritol.
Preferred polyether polyols include, but are not limited to, triols such as glycerol, trimethylolethane (i.e., 1-tris (hydroxymethyl) ethane) and trimethylolpropane (i.e., 1-tris (hydroxymethyl) propane), tetrols such as pentaerythritol, pentaols such as glucose, hexaols such as dipentaerythritol and sorbitol, or alkoxylated derivatives of all of the foregoing polyols, such as preferably ethoxylated and propoxylated derivatives thereof.
A particularly preferred polyether polyol is polyoxypropylene triol.
Other suitable polyols for the present invention include those having a low molecular weight of 30 to 400, which are preferably compounds having hydroxyl and/or amino groups and acting as chain extenders or crosslinkers. These compounds generally have from 2 to 8, preferably from 2 to 4, hydrogen atoms which are capable of reacting with isocyanates.
Suitable isocyanates for producing the flame retardant polyurethane of the present invention may be selected from, for example, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates (see, for example, w. Siefken, in julus Liebigs ANNALEN DER CHEMIE (journal of librish chemistry, 562, pages 75-136), such as those of the formula Q (NCO) r, wherein r is 2 to 4, preferably 2 to 3, Q is an aliphatic hydrocarbon group having 2 to 18 carbon atoms, preferably 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon group having 4 to 15 carbon atoms, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 13 carbon atoms, or an araliphatic hydrocarbon group having 8 to 15 carbon atoms, preferably 8 to 13 carbon atoms.
Suitable polyisocyanates for the present invention are aromatic, cycloaliphatic and/or aliphatic polyisocyanates having at least two isocyanate groups and mixtures thereof. Preferred are aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tris (4-isocyanatophenyl) methane and polymethylene-polyphenylenediisocyanate, cycloaliphatic polyisocyanates such as diphenylmethane diisocyanate, toluene diisocyanate, aliphatic polyisocyanates and hexamethylene diisocyanate, isophorone diisocyanate, dimeric (dimeryl) diisocyanate, 1-methylenebis (4-isocyanatocyclohexane-4, 4' -diisocyanatodicyclohexylmethane (met) and isomeric mixtures thereof, 1, 4-cyclohexyldiisocyanate and lysine diisocyanate and mixtures thereof.
Particularly preferred are generally the industrially readily available polyisocyanates, such as 2, 4-and 2, 6-toluene diisocyanate, and diphenylmethane isocyanate (MDI) or polymeric forms thereof (pMDI).
For the purposes of the present invention, flame-retardant polyurethanes can be linear PURs, for example produced by means of diols and diisocyanates, or crosslinked PURs, for example produced by conversion of triisocyanate diisocyanate mixtures with triol-diol mixtures. The properties of flame retardant polyurethanes can vary within wide limits. Depending on the degree of crosslinking and/or the isocyanate or OH component used, thermosets, thermoplastics or elastomers are obtained.
The flame retardant polyurethane of the present invention may be a flame retardant polyurethane foam for use as a flexible or rigid foam, or as a molding compound for molding, as a casting resin (isocyanate resin), as (textile) elastic fibers, polyurethane coating and as polyurethane adhesive.
The present invention also provides a flame retarded polyurethane foam obtained by reacting a polyol and an isocyanate in the presence of a flame retardant comprising a phosphinate of formula (I), further in the presence of a blowing agent, a blowing catalyst, a foam stabilizer and optionally other additives.
In a preferred embodiment of the present invention, the flame retardant polyurethane foam of the present invention is a flexible foam.
In another preferred embodiment of the present invention, the flame retardant polyurethane foam of the present invention is a rigid foam.
For the purposes of the present invention, the term "blowing agent" refers to a substance capable of providing a gas in a polyol-isocyanate reaction and producing a foam having a cellular structure. Any conventional blowing agent used to produce polyurethane foam is suitable for this purpose, including physical blowing agents and chemical blowing agents. Examples of physical blowing agents include butane and carbon dioxide, which expand under reduced pressure, and short chain (C 5-C6) aliphatic molecules, such as pentane or cyclopentane, and various hydrofluoroolefins, such as 1, 3-tetrafluoropropene, which are low boiling liquids. Examples of chemical blowing agents include water and carboxylic acids, which release gas upon reaction with isocyanate. A particularly preferred blowing agent is water.
For the purposes of the present invention, suitable blowing catalysts for producing the flame-retardant polyurethane foams of the present invention are preferably selected from amine catalysts (e.g., tertiary amines) and organometallics (e.g., stannous octoate, stannous acetate, dibutyltin diacetate, etc.).
For the purposes of the present invention, suitable foam stabilizers for producing flame retarded polyurethane foams can be any conventional stabilizer for controlling and stabilizing polyurethane foams. As a preferred example, the stabilizer may be selected from silicone surfactants.
To produce flame retardant polyurethane foams according to the present invention, other additives may be added to the reactant mixture, including fillers, pigments, light stabilizers, and processing aids.
The invention also relates to the use of flame retardant polyurethane or flame retardant polyurethane foam as described above for the manufacture of door liners, headliners, seat covers, high resilience foam seats, high resilience foam mattresses, rigid foam insulation panels, viscoelastic foam mattresses, potting foam for battery applications, microcellular foam seals and gaskets, durable elastomeric wheels and tires, automotive suspension bushings, electro-potting compounds, high performance adhesives, surface coatings and sealants, synthetic fibers, carpet liners, hard plastic parts and hoses.
The invention also relates to the use of flame retardant polyurethane or flame retardant polyurethane foam for the manufacture of electrical switching components, components in automotive construction, electrical engineering or electronics, printed circuit boards, prepregs, potting compounds for electronic components, for marine and rotor blade construction, for outdoor GFRP applications, household and hygiene applications and in engineering materials.
Detailed Description
Examples
Hereinafter, the present invention is described in more detail and in detail with reference to examples, which are not intended to limit the present invention.
1. The components used are as follows:
Flame retardant:
FR-1 Ethyl (meth) phosphinate (MEPE) product of Synthesis example 1
FR-2 Synthesis example 2 butyl methylphosphinate product
FR-3 Synthesis example 3 butyl (meth) phosphinate (MUPU) product
Ref-1-Fyrol PCF from ICL Industrial Products, TCPP (tris (1-chloro-2-propyl) phosphate), a halogenated phosphate
Ref-2 Exolit OP 550 from Clariant International Ltd, a halogen-free polymeric phosphorus-containing polyol specially designed for flexible polyurethane foam, is a phosphate ester with hydroxyalkyl groups.
Polyol:
Polyether polyol (P1) Arcolcube 1104 or 1108 from Covestro AG, medium molecular weight polyoxypropylene triol having OH number of 56 mg KOH/g
Polyester polyol (P2) A rate cube HT 5510, an aromatic polyester polyol from the Stepan Company having a hydroxyl number of 257 mg KOH/g
Polymerization catalyst:
Cat 1-Kosmos cube EF from Evonik Industries, stannous catalyst
Cat 2-Kosmos cube 29 from Evonik Industries stannous octoate catalyst
Cat 3 Niax A1 from Momentive Performance Materials Inc., bis (2-dimethylaminoethyl) ether based amine catalyst
Cat 4-Tegoamin:33 from Evonik Industries, triethylenediamine-based amine catalyst
Cat 5 JEFFFCAT zF-10 from Huntsman, amine catalyst based on N, N, N '-trimethyl-N' -hydroxyethyl diaminodiethyl ether
Cat 6 Polycat 5 from Evonik Industries, bis (2-dimethylaminoethyl) methylamine based amine catalyst
Cat 7-Kosmos 75 MEG from Evonik Industries foam catalyst based on Low viscosity Potassium octoate
Foam stabilizer:
S1 Tegostab B8232, organosilicon surfactant from Evonik Industries
S2 Tegostab B8522 from Evonik Industries, organosilicon surfactant
TDI (toluene diisocyanate):
T80 Desmodur T80,2, 4-and 2, 6-toluene diisocyanate from Covestro AG, 80/20 isomer mixture
MDI (diphenylmethane diisocyanate):
MDI 1-Desmodur from Covestro AG, 44V 70L, which is a mixture of diphenylmethane-4, 4' -diisocyanate (MDI) with isomers and higher-functionality homologs (PMDI).
2. Synthetic examples of flame retardants FR-1, FR-2 and FR-3 according to the invention
2.1 Synthesis example 1 preparation of FR-1
Step 1 preparation of diethyl methylphosphonite
A 25L autoclave equipped with a thermometer and condenser was charged with a mixture of 5280 g petroleum ether, 413 g absolute ethanol and 1100 g triethylamine. The reaction system was purged three times with nitrogen and then a solution of 501 g of methyldichlorophosphine (methyldichlorophosphane) was added dropwise at a temperature of 25 ℃. Once the addition was complete, the temperature was maintained at 25 ℃ for 30 minutes.
The resulting reaction mixture was then pressure filtered to remove NEt 3. HCl formed. The filter cake obtained is washed with 1000 ml of petroleum ether. Subsequently, the filtrate weighing 6590 g was distilled to recover petroleum ether and obtain a crude product of diethyl methylphosphonite.
Finally 557.8 g of diethyl methylphosphonite are obtained by rectification. Purity by Gas Chromatography (GC) was 98.5% giving a 96.1% yield.
Step 2 preparation of ethyl (methyl) phosphinate (FR-1)
A1L three-necked flask equipped with a thermometer and condenser was charged with a mixture of 557.0 g of diethyl methylphosphonite and 27.50 g of p-toluenesulfonate. The flask was then purged with N 2. The temperature was gradually increased and the reaction mixture was vigorously stirred and refluxed. The oil temperature was slowly raised from 120 ℃ to 170 ℃ prior to insulation. After 9 hours, no significant reflux (less than 0.5% of starting material detected by GC) was observed, indicating that the reaction was complete.
Finally, 535.0 g of FR-1 product having a viscosity of 3.5 mPa.s are obtained by vacuum distillation (2 to 3 kPa,101 ℃). The purity of the product, as determined by GC, was 98% giving a yield of 98%.
2.2 Synthesis example 2 preparation of FR-2
Methyl dichlorophosphine was continuously fed to the vaporizer at a rate of 119.39 g/h. The vaporized methyl dichlorophosphine was then transferred to a column continuous reactor at a rate of 80 mL/min using a nitrogen stream.
At the same time, 99.5% n-butanol was introduced into another vaporizer at a rate of 243 g/h. The vaporized butanol was purged into the column reactor using a nitrogen stream, also at a rate of 80 mL/min. The vaporized methyldichlorophosphine and n-butanol are then reacted rapidly in a column reactor.
The resulting light fraction of chlorobutane produced by the rapid reaction was condensed and collected in a low boiling point substance receiving bottle. The heavy fraction of crude butyl methylphosphinate formed during the reaction process was collected in a separate receiving bottle and subsequently neutralized with triethylamine.
After neutralization, n-butanol is removed by vacuum distillation. This procedure gives 96.0% of butyl methylphosphinate having a viscosity of 3.4 mPa s and a purity of 98.5% obtained by rectification.
2.3 Synthesis example 3 preparation of FR-3
Step 1 preparation of dibutyl methylphosphonite
A mixture of 6200 g of petroleum ether, 674 g of dry n-butanol and 910 g of triethylamine was charged into a 25L autoclave equipped with a thermometer and a condenser. The reaction system was purged three times with nitrogen and then 507 grams of a solution of methyldichlorophosphine was added dropwise at a temperature of-10 ℃. Once the addition was complete, the temperature was maintained at 0 ℃ for 30 minutes.
The resulting reaction mixture was then pressure filtered to remove NEt 3. HCl formed. The filter cake obtained is washed with 1000 ml of petroleum ether. Subsequently, the filtrate weighing 7506 g was distilled to recover petroleum ether and obtain a crude product of dibutyl methylphosphonite.
Finally 756.7 g of dibutyl methylphosphonite are obtained by rectification. Purity by Gas Chromatography (GC) was 95% giving 88% yield.
Step 2 preparation of butyl (methyl) phosphinate (FR-3)
In a 1L three-necked flask equipped with a thermometer and a condenser, a mixture of 600 g of dibutyl methylphosphonite and 30 g of p-toluenesulfonate was added. The flask was then purged with N 2. The temperature was gradually increased and the reaction mixture was vigorously stirred and refluxed slightly. The oil temperature was slowly raised from 150 ℃ to 180 ℃ prior to insulation. After 6 hours, the starting material detected by GC was less than 0.5%, indicating that the reaction was complete.
Finally, 571 g of FR-3 product with a viscosity of 6.4 mPa. Multidot.s were obtained by vacuum distillation (0.2-0.3 kPa,86 ℃). The purity of the product, as determined by GC, was 98% giving a yield of 98.0%.
3. Hydrolytic stability comparative test
The hydrolytic stability provided by different flame retardants is compared by measuring the acid number over time during storage of a polyol blend containing the flame retardant and water at elevated temperatures. For this purpose, 90 g of polyol, 9g of flame retardant and 4.5 g of water were homogenized by stirring at 1500 rpm for 2 minutes. The acid number was then determined using a 3:1 (v/v) isopropanol/water mixture as solvent and a 0.1N NaOH (water) solution as titrant. The samples were then stored at 40 ℃ and the acid numbers were determined after 11, 17 and 28 days. The samples were homogenized by stirring at 1500 rpm for 2 minutes prior to analysis. The development of acid numbers of the polyol-water blends without added flame retardant was also determined after 11 days and 28 days, respectively, as shown in table 1.
TABLE 1 comparison of hydrolytic stability acid number evaluation over time of polyol blends containing flame retardant and water during storage at 40C
Example FR-1 of the present invention did not cause a significant increase in the acid number in its polyol blend over and after storage at 40 ℃ for 28 days, as compared to the reference without flame retardant. This indicates a high hydrolytic stability of FR-1 during storage in the polyol blend, i.e., hydrolysis of FR-1 is zero to negligible. In contrast, the acid number of the polyol blend containing Ref-2 increased significantly after only 11 days under the same storage conditions, which can only be explained by hydrolysis of Ref-2.
4. Viscosity comparison of polyol-flame retardant mixtures
As mentioned above, the viscosity of the liquid flame retardant of the present invention is advantageously low, which facilitates easy processing and handling in industrial applications. In the synthetic examples provided, FR-1 and FR-2 both have a viscosity of less than 5 mPa s, FR-3 has a viscosity of less than 7 mPa s, and TCPP (Ref-1) generally has a viscosity ten times higher (60-70 mPa s) at room temperature, measured by DIN 51398.
In Table 2 below, a comparison is made between the viscosity of the pure polyol (P2) and the mixture of polyol (P2) and flame retardant (FR-1, FR-2, FR-3 or Ref-1). Polyol-flame retardant mixtures were prepared by combining polyol P2 with specific flame retardants (FR-1, FR-2, FR-3 or Ref-1) at a weight ratio of 89.5:10.5 at room temperature. The mixture was thoroughly blended at 1000 rpm for 1 minute using a mechanical stirrer to ensure homogeneity. The dynamic viscosity of the pure polyol and polyol-flame retardant mixture was then measured in accordance with DIN 51398.
TABLE 2 viscosity of the neat polyol and polyol-flame retardant mixture at room temperature
From the data in table 2, it is observed that the liquid flame retardant of the present invention has additional advantages over conventional liquid flame retardants, such as TCPP (Ref-1), in effectively reducing the viscosity of the polyol-flame retardant mixture during the blending process. This advantageous property may further enhance the overall processability when used in polymer manufacture.
5. Soft Polyurethane (PUR) foam formulations and performance testing
The stannous catalyst, polyol, flame retardant, water, foam stabilizer and amine catalyst were weighed into a dry beaker in this order and pre-mixed for 60 seconds at 500 rpm (for polyether polyol formulations) or 1000 rpm (for polyester polyol formulations), respectively. After the addition of TDI, the mixture was stirred at 2500 rpm for 7 seconds. The resulting mass was poured rapidly into a paper liner box mold (25 x 26 cm). The rise time and further observations were recorded during the foaming process. The foam was cured at room temperature for about 16 hours, then cut and collected in each of the comparative examples (C1-C3) or examples (I1-I2) of the present invention for further evaluation.
The selection of polymerization catalyst, foam stabilizer and TDI for each foam example was guided in each case based on the prior experience of optimal foamability, the details being set forth in table 3 below.
TABLE 3 polyol, flame retardant, catalyst, foam stabilizer & TDI for each PUR foam example
Evaluation of flame retardancy of Soft foam (FMVSS 302)
The efficiency of the flame retardant was evaluated by testing the combustion behavior of a sample of flexible polyurethane foam containing the flame retardant with a target density of 30 kg/m 3 in a horizontal burn test, as described in Federal Motor VEHICLE SAFETY STANDARD (FMVSS 302). The foam density in the examples was measured according to DIN 53420. According to this criterion, the sample is given the highest rating (SE, "self-extinguishing") if the flame does not travel beyond the 38 mm mark on the specimen but extinguishes within that distance. Lower grades include SE/NBR (self-extinguishing/no burn rate), SE/B (self-extinguishing/burn rate) and B (burn rate). 5 sample specimens were cut from each foam and the test was performed. The lowest rated test specimen determines the overall grade of foam.
The flame retardancy of the tested flexible foam examples is compared in table 4.
TABLE 4 Performance data for Flexible polyurethane polyether (P1) foam formulations
* The amounts of all components are given in parts per 100 parts by weight polyol (php).
As demonstrated by the performance data set forth in table 4, comparative example C1 (polyether polyurethane foam without flame retardant additives) did not meet the desired flame retardant criteria. With the halogenated reference flame retardant TCPP (Ref-1) of 12 php, comparative example C2 provides a polyether polyurethane foam that meets the desired flame retardancy. When an attempt was made to reduce the amount of flame retardant to 8 php TCPP, as shown in comparative example C3, it was found that the amount of flame retardant was insufficient and the resulting foam did not reach the optimal flame retardancy (SE).
Example I1 of the present invention demonstrates the effectiveness of the halogen-free flame retardant (FR-1) of the present invention in achieving the optimum flame retardancy standard for polyether polyurethane foams, even at low loadings of only 4 php.
Example I2 of the present invention, a polyether polyurethane foam having 4 php of the halogen-free flame retardant of the present invention (FR-2), exhibited as excellent a flame retardant rating as I1.
6. Rigid Polyisocyanurate (PIR) foam formulations and performance tests
The octanoate catalyst, polyol, flame retardant, water, foam stabilizer, and amine catalyst were weighed into a dry beaker in this order and pre-mixed at 1000 rpm for 50 seconds. After the addition of n-pentane, the mixture was stirred at 1000 rpm for 10 seconds to incorporate it into the mixture. MDI is then added to the mixture and the liquid is mixed at 2500 rpm for 7 seconds. The resulting mass was poured rapidly into a paper liner box mold (25 x 26 cm). The rise time and further observations were recorded during the foaming process. The foam was cured at room temperature for about 16 hours, then cut and collected in each comparative example (C4-C6) or example (I3-I4) of the present invention for further evaluation.
The selection of the polymerization catalyst, foam stabilizer and MDI for each rigid foam example was guided in each case based on the prior experience of optimal foamability, the details being set forth in table 5 below.
TABLE 5 polyols, flame retardants, catalysts, foam stabilizers and MDI for PIR foam examples
Flame-retardant evaluation method for rigid foams (DIN 4102-1)
DIN4102-1 classifies the building materials according to their flammability. The effective standard is divided into two fire classes. "A" represents a non-combustible material and "B" represents a combustible material. Grade B is associated with polyurethane foams, such as PIR-insulation panels. It is then subdivided into levels of b1=low flammability; b2=normal flammability; b3=high flammability. For reference, the building foam system in most spray cans sold in germany corresponds to building material class B2. The main grading criterion for the flammability class B2 is the flame height in the vertical burn test, which needs to be kept below the maximum value of 150 mm, which is an ideal criterion for the benchmark of flame retardancy of building materials.
The flame retardancy of the different rigid PIR foam samples was evaluated using DIN4102-1 and is listed in table 6 below.
TABLE 6 Performance data for rigid polyisocyanurate polyester (P2) foam formulations
* The amounts of all components are given in parts per 100 parts by weight polyol (php).
As demonstrated by the performance data set forth in table 6, comparative example C4 (PIR foam without the flame retardant additive) failed to meet the desired flame retardant standard rating B2. Comparative example C5 represents a rigid PIR foam having the desired flame retardant rating by incorporating 15 php of the halogenated reference flame retardant TCPP (Ref-1). However, when an attempt was made to reduce the amount of such halogenated flame retardant to 12 php TCPP, as demonstrated in comparative example C6, such reduced flame retardant content was observed to be insufficient, resulting in the foam failing to achieve the desired flame retardancy rating.
Example I3 of the present invention demonstrates the excellent flame retardancy achieved by incorporating the same amount of the halogen-free flame retardant FR-1 of the present invention of 12 php into a rigid PIR foam, meeting the optimum flame retardancy criteria.
Similarly, inventive examples I4 and I5 achieved equally excellent flame retardant ratings by substituting FR-1 with the same amount of FR-2 or FR-3, respectively, as in I3. This further highlights the effectiveness of the halogen-free flame retardant of the present invention in achieving the desired level of flame retardancy in a rigid foam.
Claims (15)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310599807.0A CN116621873A (en) | 2023-05-25 | 2023-05-25 | A method for preparing ethyl methyl ethyl phosphinate and aluminum salt of methyl ethyl phosphinate |
| CN2023105998070 | 2023-05-25 | ||
| CNPCT/CN2023/115548 | 2023-08-29 | ||
| CN2023115548 | 2023-08-29 | ||
| PCT/CN2024/083608 WO2024239791A1 (en) | 2023-05-25 | 2024-03-25 | Flame-retardant polyurethane and uses thereof |
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| KR (1) | KR20260015905A (en) |
| CN (1) | CN121219302A (en) |
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Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914345A (en) | 1971-01-08 | 1975-10-21 | Hoechst Ag | Process for the manufacture of dialkyl-phosphinic acid esters |
| DE2832253A1 (en) | 1978-07-22 | 1980-01-31 | Bayer Ag | METHOD FOR PRODUCING MOLDED FOAMS |
| US4458035A (en) | 1981-11-04 | 1984-07-03 | Stauffer Chemical Company | Polyurethane foam having a flame retardant oligomeric phosphate ester |
| DE3435070A1 (en) | 1984-09-25 | 1986-04-03 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING OPTIONALLY FOAMED POLYURETHANES, WHICH HAVE BEEN CONNECTED OR MADE-UP WITH ANOTHER MATERIAL |
| DE19616025C1 (en) * | 1996-04-23 | 1997-04-17 | Hoechst Ag | Simple, direct prepn. of aluminium phosphinate(s) from alkyl ester |
| DE19923619C2 (en) * | 1999-05-25 | 2001-08-23 | Clariant Gmbh | Process for the preparation of dialkylphosphinic acids and their salts |
| US7288577B1 (en) | 1999-09-09 | 2007-10-30 | Supresta U.S. Llc | Polyurethane foam containing flame retardant blend of non-oligomeric and oligomeric flame retardants |
| EP2021433B1 (en) | 2006-05-15 | 2016-02-03 | Bromine Compounds Ltd. | Flame retardant composition |
| DE102008055914A1 (en) | 2008-11-05 | 2010-05-06 | Clariant International Limited | A process for the preparation of mono-hydroxy-functionalized dialkylphosphinic acids, esters and salts by means of acroleins and their use |
| DE102008056341A1 (en) | 2008-11-07 | 2010-05-12 | Clariant International Limited | Process for the preparation of mono-amino-functionalized dialkylphosphinic acids, esters and salts by means of acrylonitriles and their use |
| DE102008056342A1 (en) | 2008-11-07 | 2010-05-12 | Clariant International Limited | Process for the preparation of dialkylphosphinic acids, esters and salts by means of acrylonitriles and their use |
| CN104693238A (en) | 2015-03-26 | 2015-06-10 | 洪湖市一泰科技有限公司 | Preparing method for dialkyl group phosphinic acid alkyl ester and dialkyl phosphinate salt |
| CA3070601A1 (en) * | 2017-07-24 | 2019-01-31 | Icl-Ip America Inc. | Rigid polyurethane foam containing reactive flame retardant |
| CN107799841A (en) * | 2017-10-19 | 2018-03-13 | 江汉大学 | Dialkyl phosphinic acid fat fire retardant, lithium-ion battery electrolytes and lithium ion battery containing the fire retardant |
| CN109400643A (en) | 2019-01-02 | 2019-03-01 | 利尔化学股份有限公司 | Methylethyl phosphinicacid ethyl ester and Methylethyl phosphinic acids aluminium salt preparation process |
| CN112028932B (en) * | 2020-09-27 | 2022-03-15 | 江苏利思德新材料有限公司 | Dialkyl phosphinate flame retardant and preparation method and application thereof |
| CN113493478A (en) | 2021-07-28 | 2021-10-12 | 南通江山农药化工股份有限公司 | MPE synthesis process and MPE |
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