KR20210034061A - New composition and method for preparing alkoxylated triazine-arylhydroxy-aldehyde condensate - Google Patents

Abstract

Embodiments described herein generally relate to methods and chemical compositions of triazine-arylhydroxy-aldehyde condensates. In one embodiment, the triazine-arylhydroxy-aldehyde condensate reacts with an alkoxylating agent to form an alkoxylated triazine-arylhydroxy-aldehyde condensate.

Description

New composition and method for preparing alkoxylated triazine-arylhydroxy-aldehyde condensate

Related application data

This application claims benefit to U.S. Application No. 16/043,871, filed July 24, 2018, the entire contents of which are incorporated herein by reference.

Field of invention

The present invention relates to a composition of an alkoxylated triazine-arylhydroxy-aldehyde condensate and a method for preparing the composition.

Polyurethane is one of the most versatile class of polymeric materials. It is particularly useful for rigid and flexible foams. Flexible polyurethane foams are used as cushioning in a variety of consumer and commercial products including bedding, furniture, car interiors, carpet underlays and packaging. Rigid polyurethane and polyisocyanurate (polyiso) foams create one of the most popular, energy efficient and versatile insulation materials in the world. Environmental health and safety, along with fire prevention, are driving change within the insulation industry. The high insulation of rigid polyurethanes is the most suitable and efficient technology to address these requirements. This global trend is driving the demand for continuous innovation throughout the polyurethane industry.

Polyurethane foams are prepared by reacting isocyanates with polyols. The polyol component is typically one or more polyols, with surfactants, catalysts, flame retardants and blowing agents together to form a foam. The polyols most commonly used in this industry are polyether polyols and polyester polyols. Each of these classes of compounds has its own advantages and disadvantages. Polyether polyols provide hydrolytic stability, low viscosity and flexibility. Aromatic polyesters are known to contribute to flame retardancy and high modulus. However, they generally have a limited functionality and a higher inherent viscosity, so in the formulations, especially in rigid PU systems, copolyols such as polyether polyols with higher functional groups must be used. . In addition, sugar-based polyols, one of the most commonly used copolyols in these formulations, do not provide fire resistance at all.

Alkoxylated phenol-aldehyde resins have been found to be useful in the manufacture of a variety of polymeric products, including polyurethane compositions and foamed products. These resins are generally referred to as novolac-based polyether polyols. The resin is prepared by reacting novolac with an alkylene oxide. Polyols of this type are known in the industry to aid in an improved reaction to fire and have the advantage of having a high aromatic content which may have a high functional group. However, formulators still require the use of other polyols along with amine based catalysts and flame retardants to achieve desirable thermal, fire and mechanical performance.

For example, the SPF (Spray Polyurethane Foam) market is one of the fastest growing polyurethane segments due to SPF's superior ability to provide high insulation, noise reduction, and the ability to retrofit existing buildings and infrastructure. However, many SPF formulations use low molecular weight organic and inorganic catalysts to provide fast reactions and use phosphate or phosphate-chlorinated additives to perform the function of meeting building regulations for fire ratings. Low molecular weight catalysts such as amines can volatilize during spray polyurethane installations that pose a health hazard. Low-molecular flame retardants, which are constantly added to these formulations, are under regulatory investigations for problems related to environmental impact.

Accordingly, there is an increasing demand for better performance rigid polyurethane foams with special flammability specifications and acceptable physical properties. There is still a need in the industry for high reactivity to isocyanates, inherent flame retardancy, polyols with high functional groups that achieve desirable properties and allow volatile amine based catalysts and low molecular weight flame retardants to be reduced or eliminated.

In one broad embodiment of the present invention, alkoxylated triazine-arylhydroxy-aldehyde condensation compounds are disclosed. The compound is a triazine-arylhydroxy-aldehyde condensate; And reacting at least one alkoxylating agent, optionally in the presence of a catalyst, comprising, consisting of, or essentially consisting of reacting, thereby forming an alkoxylated triazine-arylhydroxy-aldehyde condensation compound. It is manufactured by the method of forming. The alkoxylating agent may be an alkylene oxide alone or may be an alkylene oxide in combination with an alkylene carbonate. In further embodiments, the alkoxylating agent may be an alkylene carbonate.

In one embodiment of the present invention, a condensation product comprising a triazine-arylhydroxy-aldehyde condensate and an alkoxylating agent comprising an alkylene oxide and an optional alkylene carbonate, and a reaction mixture comprising an optional catalyst is Is provided.

In another embodiment of the present invention, an alkoxylated triazine-arylhydroxy-aldehyde condensation compound is provided.

In another embodiment of the invention, reacting the triazine-arylhydroxy-aldehyde condensate with at least one alkylene oxide alone or in combination with an alkylene carbonate, optionally in the presence of a catalyst, and an alkoxylated tree A method comprising forming an azine-arylhydroxy-aldehyde condensation composition is provided. In one embodiment, the condensation composition is free of catalysts, flame retardants, Mannich polyols, or combinations thereof. In one embodiment, the condensation composition is free of an amine catalyst.

In another embodiment of the present invention, a polymer comprising using a formulation comprising a polyisocyanate and an isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate is provided. Articles can be made from the polymer. In one embodiment, the formulation is free of catalysts, flame retardants, Mannich polyols, or combinations thereof. In one embodiment, the formulation is free of amine catalysts.

In another embodiment of the invention, forming a reaction mixture comprising a polyisocyanate and an isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate, and curing the reaction mixture Including that, a method of forming a polymer is provided. In one embodiment, the reaction mixture is free of catalysts, flame retardants, Mannich polyols, or combinations thereof. In one embodiment, there is no amine catalyst in the formulation. The method may further comprise applying the polymer to a substrate.

Embodiments of the present invention are used to prepare an alkoxylated triazine-arylhydroxy-aldehyde condensate, the alkoxylated triazine-arylhydroxy-aldehyde condensate, and a polyurethane and polyisocyanurate resin. It relates to the use of alkoxylated triazine-arylhydroxy-aldehyde condensates used.

The alkoxylated triazine-arylhydroxy-aldehyde condensate is formed by reacting a triazine-arylhydroxy-aldehyde condensate with an alkylene oxide. Alternatively, the alkoxylated triazine-arylhydroxy-aldehyde condensate is formed by reacting the triazine-arylhydroxy-aldehyde condensate with an alkylene oxide and an alkylene carbonate. In a further alternative, the alkoxylated triazine-arylhydroxy-aldehyde condensate is formed by reacting the triazine-arylhydroxy-aldehyde condensate with an alkylene carbonate.

Any suitable triazine-arylhydroxy-aldehyde condensate may be used for the reaction with the alkylene oxide, the alkylene carbonate, or both. In various embodiments, the triazine-arylhydroxy-aldehyde condensate is formed from a reaction mixture of a triazine monomer, an arylhydroxy monomer, and an aldehyde monomer. In various embodiments, the triazine-arylhydroxy-aldehyde condensate is novolac.

The triazine monomer may be a triazine compound or a triazine derivative. An example of a triazine compound is melamine, and an example of a triazine derivative is a melamine derivative.

Suitable compounds that can be used as triazine monomers are 4-methyl-1,3,5-triazine-2-amine, 2-amino-4,6-dimethyl-1,3,5-triazine, melamine, hexame Toxymethylmelamine, hexamethylolmelamine, guanamine, acetoguanamine, propioguanamine, butyroguanamine, benzoguanamine, vinylguanamine, 6-(hydroxyphenyl)-2,4-dia And compounds from the aminotriazine group such as mino-1,3,5-triazine, and combinations thereof.

The arylhydroxy monomer may be any suitable aromatic monomer having one or more hydroxyl groups per molecule, such as monohydroxy, dihydroxy or trihydroxy benzene. They can be mononuclear or dinuclear. In various embodiments, the arylhydroxy monomer is a phenolic monomer compound. Phenol monomer compounds having at least one ortho or para position available for bonding are preferred compounds. The phenolic monomer compound may be an unsubstituted compound, or a compound substituted by, for example, an alkyl group, a phenyl group, a hydroxybenzene group, an alkoxy group, and combinations and subsets thereof. The phenolic monomer compound may also include compounds having up to about 15 carbon atoms, such as up to about 8 carbon atoms. Examples of such arylhydroxy monomers include phenol, cresol, xylenol, resorcinol, catechol, hydroquinone, naphthol, dihydroxynaphthalene, biphenol, bisphenol, phloroglucinol, pyro Gallol (pyrogallol) or their derivatives include, but are not limited to.

The aldehyde monomers include compounds having one or more aldehyde functional groups (-CHO) and any compounds that produce aldehydes. The aldehyde monomer may be represented by the formula R-CHO, and R may be an aliphatic or aromatic organic functional group. The aldehyde monomer may be a dialdehyde such as glyoxal. Suitable aldehydes are formaldehyde, paraformaldehyde, acetaldehyde, i-butyraldehyde (isobutyraldehyde), benzaldehyde, acrolein, crotonaldehyde, salicylaldehyde, 4-hydroxybenzaldehyde, furfural, pyrrole. Compounds such as -2-carboxaldehyde, cinnamaldehyde, trioxymethylene, paraldehyde, terephthaldialdehyde, glyoxal, glutaraldehyde, and combinations thereof are included, but are not limited thereto.

The triazine-arylhydroxy-aldehyde condensate may include various triazine, arylhydroxy, and aldehyde combinations. In various embodiments, the condensate is melamine, phenol, and formaldehyde novolac. Further details of the triazine-arylhydroxy-aldehyde condensate and its preparation can be found in US Pat. Nos. 6,239,248 and 9,249,251, both of which are incorporated herein by reference.

The triazine-arylhydroxy-aldehyde condensate reacts with at least one alkoxylating agent to form the alkoxylated triazine-arylhydroxy-aldehyde condensate. The alkoxylating agent may be an alkylene oxide alone, or may be an alkylene oxide in combination with an alkylene carbonate. Alternatively, the alkoxylating agent may be an alkylene carbonate.

Suitable alkylene oxides are linear aliphatic alkylene oxides, branched aliphatic alkylene oxides, cyclic aliphatic alkylene oxides, aromatic alkylene oxides, alkyl aromatic alkylene oxides, alkylene oxides with ethers (commonly known as glycidyl ethers). , And alkylene oxides with esters (commonly known as glycidyl esters).

Examples of suitable alkylene oxides are ethylene oxide, propylene oxide, glycidol, styrene oxide, epichlorohydrin, butylene oxide, isobutylene oxide, cyclohexane oxide, 2,3-epoxyhexane, allyl glycidyl ether. , Methyl glycidyl ether, butyl glycidyl sulfide, glycidyl methyl sulfone, glycidyl methacrylate, glycidyl allyl phthalate, and combinations thereof. . Examples of preferred alkylene oxides include compounds selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof.

The alkylene oxide may comprise from about 5 wt% to about 90 wt% of a triazine-arylhydroxy-aldehyde condensate and at least one alkylene oxide reaction mixture. Alternatively, in one embodiment, the triazine-arylhydroxy-aldehyde condensate and the alkoxylating agent have a ratio of reactive sites to the alkoxylating agent such as alkylene oxide and/or alkylene carbonate of about 20:1 to It may exist as about 1:20.

If present, suitable alkylene carbonates include linear aliphatic alkylene carbonates, branched aliphatic alkylene carbonates, aromatic alkylene carbonates, alkyl aromatic alkylene carbonates, alkyl hydroxide carbonates, vinyl carbonates, acrylic carbonates, and ester carbonates. can do. Examples of preferred alkylene carbonates are ethylene carbonate, propylene carbonate, butylene carbonate, glycerol carbonate, styrene carbonate, 1-chloro-propylene carbonate, isobutylene carbonate cyclohexene carbonate, allyl carbonate, methacrylate carbonate, vinyl carbonate, allyl And one or more alkylene carbonates selected from the group comprising phthalate carbonates, and combinations thereof. Examples of preferred alkylene carbonates include compounds selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, and combinations thereof.

Suitable alkylene carbonates are ethylene oxide, propylene oxide, glycidol, styrene oxide, epichlorohydrin, butylene oxide, isobutylene oxide, cyclohexane oxide, 2,3-epoxyhexane, allyl glycidyl ether, methyl It can be prepared from suitable mono-epoxide compounds such as glycidyl ether, butyl glycidyl sulfide, glycidyl methyl sulfone, glycidyl methacrylate, glycidyl allyl phthalate.

The alkylene carbonate may comprise from about 5 wt% to about 50 wt% of a triazine-arylhydroxy-aldehyde condensate and at least one alkylene carbonate, and optionally at least one alkylene oxide, a reaction mixture. . Alternatively, the triazine-arylhydroxy-aldehyde condensate and at least one alkylene carbonate may be present in a ratio of about 1:1 to about 1:2 reactive sites to alkylene carbonate. In one embodiment, the alkoxylating agent may be one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and mixtures thereof.

When both the alkylene oxide and the alkylene carbonate are present, the components are from about 2 wt% to about 90 wt% of the triazine-arylhydroxy-aldehyde condensate, at least one alkylene oxide, and at least It may contain one alkylene carbonate reaction mixture. Alternatively, the triazine-arylhydroxy-aldehyde condensate and the combined component of the at least one alkylene oxide and the at least one alkylene carbonate may comprise a reactive site of about 20:1 to about 1:20 to an alkyl It may be present in a ratio of ene oxide and at least one alkylene carbonate.

In a further alternative embodiment, the alkylene carbonate may be included in about 5 wt% to about 90 wt% of the triazine-arylhydroxy-aldehyde condensate and the alkylene carbonate reaction mixture.

The reactive moiety is a phenolic hydroxyl, a primary hydroxyl, a secondary hydroxyl, a tertiary hydroxyl, an aminic hydroxyl such as a primary amine, a secondary amine, a primary aromatic amine, or a secondary aromatic amine and Likewise, it is defined as any site with an unstable proton with a pKa less than 40. The primary amine will have two reactive sites and the secondary amine will have one reactive site.

The triazine-arylhydroxy-aldehyde condensate reacts with at least one alkylene oxide to form an alkoxylated triazine-arylhydroxy-aldehyde condensate. In various embodiments, the reaction conditions can include a reaction temperature in the range of about 50°C to about 270°C. Any and all temperatures within the range of about 50° C. to about 270° C. are included herein and disclosed herein; For example, the reaction temperature may be about 100°C to about 200°C, about 140°C to about 180°C, or about 160°C to about 175°C. The reaction conditions may also include a reaction pressure in the range of about 0.01 bar to about 100 bar. Any and all pressures within the range of 0.01 bar to 100 bar are included herein and disclosed herein; For example, the reaction pressure may be about 0.1 bar to about 50 bar, about 0.5 bar to about 20 bar, or about 1 bar to about 10 bar.

The ingredients can be added together in any suitable manner. For example, the reaction can be carried out in a batch system, a continuous system, a semi-batch system or a semi-continuous system.

In various embodiments, the alkylene oxide may be slowly added to the molten triazine-arylhydroxy-aldehyde condensate, and then reacted until the alkylene oxide is consumed. In various embodiments, the alkylene oxide may be bulk charged to the molten triazine-arylhydroxy-aldehyde condensate under pressure, and reacted until a certain pressure drop or until all alkylene oxide is consumed. I can make it.

The method of the present invention can be carried out in a suitable solvent. Suitable solvents are those which dissolve the reactants and the products and are themselves inert in the process. After the reaction, such a solvent may be removed from the reaction mixture through a distillation process. Examples of solvents include, but are not limited to, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and combinations thereof. In other embodiments, the alkoxylation of the triazine-arylhydroxy-aldehyde condensate can be carried out in the presence of a reactive diluent. Examples of reactive diluents that can be used include, but are not limited to, ethylene glycol, glycerol, methanol, ethanol, propanol, butanol, and combinations thereof. Alkylene oxide can react with both the reactive diluent and the triazine-arylhydroxy-aldehyde condensate to produce a liquid material of varying viscosities.

Optionally, the reaction between the triazine-arylhydroxy-aldehyde condensate and the alkylene oxide may proceed in the presence of a catalyst. Suitable catalysts include metal hydroxides, metal carbonates, metal phosphates, tertiary amines, phosphines, transition metal bases, organic acids, inorganic acids, and combinations thereof. Examples of catalysts that can be used include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium phosphate, sodium phosphate, lithium phosphate, and Including, but not limited to, combinations thereof. Examples of organic acids include oxalic acid, formic acid, acetic acid, trifluoroacetic acid, methane sulfonic acid, salicylic acid, benzoic acid, adipic acid, or p-toluenesulfonic acid; Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and combinations thereof. The organic and inorganic acids can also be used to neutralize the reaction mixture.

In one embodiment, the formulation used to form the condensate is catalyst-free, flame retardant-free, Mannich polyol-free, or combinations thereof. In one embodiment, the condensate is free of an amine catalyst.

Organic acids such as oxalic acid, formic acid, acetic acid, trifluoroacetic acid, methane sulfonic acid, salicylic acid, phosphoric acid, benzoic acid, adipic acid or p-toluenesulfonic acid can be used to neutralize the reaction mixture. If present, the catalyst may comprise from about 0.05 wt% to about 5 wt% of the triazine-arylhydroxy-aldehyde condensate and at least one alkylene oxide reaction mixture.

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensation compound may be represented by the following formula (I):

Formula I

The R ₆ functional group is represented by Formula II or Formula III. The R ₇ functional group of Formula I may be a hydrogen atom or may be represented by Formula II or Formula IV.

R ₈ and R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydroxyphenyl group, -NH (Formula IV), -N (Formula IV) ₂ , -NH ( Formula II), -N (Formula II) (Formula IV), -N (Formula II) ₂ , -NH (Formula III), -N (Formula III) (Formula IV), -N (Formula III) ₂ , NH It may be (Chemical Formula V), -N (Chemical Formula IV) (Chemical Formula V), -N (Chemical Formula V) ₂ , or -NH ₂ .

Structures of Formulas II, III, IV, and V are shown below.

Formula II

Formula III

Formula IV

Formula V

In the above formulas, R ₁ and R ₂ are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, or an alkyl group having 1 to 4 carbon atoms containing a hydroxyl group;

R ₁₀ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms containing a hydroxyl group, a phenyl group, a vinyl group, a propenyl group, a phenyl group containing hydroxyl, a pyrrole Group, or furanyl group.

R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxybenzene group, or 1 to 10 carbon atoms. And at least one carbon is i) a hydroxyl group, ii) a hydroxybenzene group, or iii) an alkyl group substituted by a phenyl group. In various embodiments, R ₁₁ and R ₁₂ together can form a common aromatic ring with or without a hydroxyl group.

R ₁₃ and R ₁₄ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydroxyphenyl group, -NH (Formula IV), -N (Formula IV) ₂ , -NH (Formula IV), -N ((Formula II) (Formula IV)), -N (Formula IV) ₂ , or -NH ₂ .

R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydroxyphenyl group, -NH (Formula IV), -N (Formula IV) ₂ , -NH (Chemical Formula V), -N (Chemical Formula IV) (Chemical Formula V), -N (Chemical Formula V) ₂ , or -NH ₂ .

In the above formula, when alkylene carbonate is used as the sole alkoxylating agent, each m is independently 1 to 10, each n is independently 0 to 10, each x is independently 3 to 10, and each x'is Independently from 3 to 10. The monomers represented by m and n may be arranged in any order, combination or subcombination.

In the above formula, when the alkylene oxide is the only alkoxylating agent, each m is independently 1 to 10, each n is independently 0 to 10, each x is independently 1 to 20, and each x'is independently 1 to 20. The monomers represented by m and n may be arranged in any order, combination or subcombination. In other embodiments, when the alkylene oxide is the only alkoxylating agent, each x is independently 1 to 2, and each x′ is independently 1 to 2. In another embodiment, when an alkylene oxide is supplied to the reaction mixture to prepare a block copolymer structure and the alkylene oxide is the only alkoxylating agent, each x is independently 3 to 20, and each x'is independently 3 to It is 20. The monomers represented by m and n may be arranged in any order, combination or subcombination.

In the above formula, when both alkylene oxide and alkylene carbonate are used as the alkoxylating agent, each m is independently 1 to 10, each n is independently 0 to 10, and each x is independently 1 to 20, and each x'is independently 1 to 20. The monomers represented by m and n can be arranged in any order, combination, or subcombination. In another embodiment, when both alkylene oxide and alkylene carbonate are used as the alkoxylating agent, each x is independently 1 to 2, and each x'is independently 1 to 2. In another embodiment, when alkylene carbonate and alkylene oxide are used as the alkoxylating agent, each x is independently 3-20, and each x'is independently 3-20. In another embodiment, when the alkoxylating agent is a combination of an alkylene oxide and an alkylene carbonate, the average of all x and x′ is greater than 2, and the average of all x and x′ is greater than 2.

The alkoxylated triazine-arylhydroxy-aldehyde condensate generally has a nitrogen content of about 0.5 wt% (weight percent) to about 41 wt%, such as about 1 wt% to about 23 wt%, for example For example, in various other embodiments, from about 5 wt% to about 15 wt%.

The alkoxylated triazine-arylhydroxy-aldehyde condensate generally has an aromatic content of about 0.5 wt% (weight percent) to about 69 wt%, such as about 5 wt% to about 40 wt%, for example For example, in various other embodiments, from about 12 wt% to about 30 wt %.

Examples of the alkoxylated triazine-arylhydroxy-aldehyde condensate are represented by the following formulas VIa-VIh:

Formula VIa

Formula VIb

Formula VIc

,

,

Formula VId

,

,

Formula VIe

,

,

Formula VIf

,

,

Formula VIg

, 및

, And

Formula VIh

.

.

The alkoxylated triazine-arylhydroxy-aldehyde condensate of the present invention generally has a viscosity of about 0.01 Pascal seconds to 60 Pascal seconds at 25°C, such as about 0.01 Pascal seconds to 30 Pascal seconds at 25°C. Has. Any and all ranges within 0.01 to 60 pascal seconds are included herein and disclosed herein, for example, the alkoxylated triazine-arylhydroxy-aldehyde condensate in a solvent is 0.1 to 30 pascals at 25° C. Seconds or in the range of 10 to 20 pascal seconds. The alkoxylated triazine-arylhydroxy-aldehyde condensate of the present invention may additionally exhibit non-newtonian behavior such as shear thinning behavior, which is a type of alkoxylation agent. And the number of x and x'introduced through the alkoxylation agent.

The preparation of the triazine-arylhydroxy-aldehyde condensation product and the formation of the alkoxylated triazine-arylhydroxy-aldehyde condensation composition may be carried out in the same reactor or in different reactors. Preparation of the triazine-arylhydroxy-aldehyde condensation product and/or the formation of the alkoxylated triazine-arylhydroxy-aldehyde condensation composition may be carried out in a continuous, semi-continuous, semi-continuous-batch, or batch-type process and/or reactor. Can be done.

The alkoxylated triazine-arylhydroxy-aldehyde condensate of the present invention can be used as a polyisocyanate-reactive compound to prepare polyurethane and polyisocyanurate-based polymers.

In one embodiment, a formulation referred to herein as a reaction mixture comprising a polyisocyanate and an isocyanate reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate as described herein is prepared. Can be used to make polymers. The polyisocyanate component may also be referred to as “A Side” in the polyurethane reaction process. The isocyanate-reactive compound component, such as the alkoxylated triazine-arylhydroxy-aldehyde condensate described herein alone or in combination with other polyols, may be used in the polyurethane reaction process as "B side". May also be referred to as ". In one embodiment, the formulation or reaction mixture is free of catalysts, flame retardants, Mannich polyols, or combinations thereof. In one embodiment, the formulation is free of amine catalysts.

The at least one polyisocyanate may contain about 33 wt. To about 83 wt., such as about 49 wt. To about 51 wt., wherein the isocyanate-reactive compound comprises about 13 wt. To about 51 wt., such as about 38 wt. To about 40 wt., wherein the total amount of components is equal to 100 wt% of the reaction mixture. The reaction mixture may further comprise optional additive materials as described herein, and if present, about 4 wt. To about 16 wt%, such as about 11 wt. To about 13 wt%, wherein the total amount of components equals 100 wt% of the reaction mixture.

In various embodiments, the reaction mixture is formed with at least one polyisocyanate and at least one alkoxylated triazine-arylhydroxy-aldehyde condensate.

Suitable polyisocyanates include diisocyanates, triisocyanates, and combinations thereof. Examples of suitable polyisocyanates are m-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-di Isocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate , Diphenylmethane-2,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4, 4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4',4"-triphenyl methane triisocyanate, polymethylene polyphenyl isocyanate, polymeric diphenyl Methane diisocyanate (PMDI), isophorone diisocyanate, toluene-2,4,6-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, isophorone diisocyanate , Hexamethylene-1,6-diisocyanate, polymethylene polyphenylisocyanate, and combinations thereof Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4- Diisocyanates, and mixtures thereof, are generally referred to as MDI and may be used Any polymeric form of the above compounds may also be used, for example polymeric diphenylmethane diisocyanate (PMDI) may be used Toluene-2,4 -Diisocyanate, toluene-2,6-diisocyanate, and mixtures thereof are generally referred to as TDI and can all be used.

Polyisocyanates of any of the foregoing can be modified to include urethanes, ureas, biurets, carbodiimides, allofonates, uretonimines, isocyanurates, amides, or similar linkages. . Examples of modified isocyanates of this type include various urethane groups and/or urea group-containing prepolymers and so-called'liquid MDI' products and the like.

In various embodiments, the polyisocyanate may be a blocked isocyanate, wherein the standard polyisocyanate has been pre-reacted with a blocking agent containing an active hydrogen group, and then greater than 40°C (typically in the range of 100°C to 190°C). It can be deblocked at temperature. Examples of blocking agents include, but are not limited to, γ-caprolactam, phenol, methyl ketone oxime, 1,2,4-triazole, dimethyl malonate, and combinations thereof.

The isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate may further comprise one or more additional polyols.

Polyols that can be used with the alkoxylated triazine-arylhydroxy-aldehyde condensate include polyether polyols. These can be produced by polymerizing an alkylene oxide on an initiator compound having a plurality of active hydrogen atoms. Suitable initiator compounds are alkylene glycol, glycol ether, glycerin, trimethylolpropane, sucrose, glucose, fructose, phenol formaldehyde condensate, ethylene diamine, hexamethylene diamine, diethanolamine, monoethanolamine, piperazine, amino Ethylpiperazine, diisopropanolamine, monoisopropanolamine, methanol amine, dimethanolamine and toluene diamine. An example of such a polyol is Poly-G 74-376, a sucrose initiated polyether polyol made from ethylene oxide and propylene oxide commercially available from Monument Chemical.

Polyester polyols can also be used as part of the isocyanate reactive compound. Polyester polyols comprise the reaction product of a polyol, usually a diol and a polycarboxylic acid or an anhydride thereof, usually a dicarboxylic acid or dicarboxylic acid anhydride. The polycarboxylic acid or anhydride may be aliphatic, alicyclic, aromatic, and/or heterocyclic. An example of such a polyol is Terol 250, an aromatic polyester polyol commercially available from Huntsman Corporation.

The isocyanate-reactive compound may also include Mannich polyols. Especially in spray foam applications, the Mannich polyols best established in the formulation are the reaction products of nonyl phenol, formaldehyde and diethanolamine. Manufacturers of Mannich polyols provide flexibility in formulations by varying the proportions of formaldehyde, ethanolamine and alkoxylate to provide specific functional groups and equivalents. The Mannich polyol used as one of the reference polyols in the examples herein is also nonyl phenol initiated. In other embodiments, the isocyanate-reactive compound may be free of Mannich polyols. An example of a Mannich polyol is Jeffol R-470X, commercially available from Huntsman Corporation.

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensate is present in the isocyanate-reactive compound in a range from about 1 weight percent to about 50 weight percent. Any and all ranges between 1 and 50 weight percent are included herein and disclosed herein; For example, the alkoxylated triazine-arylhydroxy-aldehyde condensate is the isocyanate-reactive compound in the range of 5% to 35%, 15% to 25%, or 9% to 21% by weight. Can exist in

In various embodiments, it has been observed that the alkoxylated triazine-arylhydroxy-aldehyde condensate has a sufficiently high reactivity that the catalyst is selective. The reactant and/or reaction mixture of the alkoxylated triazine-arylhydroxy-aldehyde condensate and polyisocyanate compound may be free of a catalyst such as an amine catalyst. Additionally, the reactant and/or reaction mixture of the alkoxylated triazine-arylhydroxy-aldehyde condensate and polyisocyanate compound may be free of catalysts, flame retardants, Mannich polyols, or combinations thereof.

In one embodiment, the mixture of the polyisocyanate and the alkoxylated triazine-arylhydroxy-aldehyde condensate further comprises a phosphorus-containing flame retardant, a diluent, a catalyst, or combinations thereof. In one embodiment, the mixture of the polyisocyanate and the alkoxylated triazine-arylhydroxy-aldehyde condensate further comprises a cell opener, a surfactant, a blowing agent, and combinations thereof.

In various embodiments, it has been observed that the alkoxylated triazine-arylhydroxyl-aldehyde condensate has sufficient reactivity so that the addition of a catalyst to the polymer formation reaction is not required. The mixture of the polyisocyanate and the alkoxylated triazine-arylhydroxy-aldehyde condensate may be free of catalysts, flame retardants, Mannich polyols, or combinations thereof. In one embodiment, the mixture of the condensate may not have an amine catalyst.

Optionally, in various embodiments, the mixture of the polyisocyanate and alkoxylated triazine-arylhydroxy-aldehyde condensate may also include a catalyst. Examples of catalysts include tertiary amines such as dimethylbenzylamine, 1,8-diaza (5,4,0)undecan-7, pentamethyldiethylenetriamine, dimethylcyclohexylamine and triethylene diamine, It is not limited thereto. Potassium salts such as potassium acetate and potassium octoate can also be used as catalysts. In various embodiments, the alkoxylated triazine-arylhydroxyl-aldehyde condensate minimizes the use of a catalyst through its inherent high reactivity (autocatalytic) to isocyanates, or is incorporated as described herein. Make sure there is no catalyst in the simulation.

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensate also contains a diluent. Suitable diluents include, but are not limited to, polyglycols, etherified polyglycols, dibasic esters of acids, and combinations thereof. Examples of diluents include ethylene glycol, glycerol, diethylene glycol, monomethyl ether of ethylene glycol, dimethyl ether of ethylene glycol, diethyl adipate, dimethyl adipate, diethyl succinate, dimethyl succinate, and combinations thereof. , But is not limited thereto.

Depending on the particular type of polymer being prepared and the required properties of the polymer, a wide variety of additional substances may be present during the reaction of the polyisocyanate compound with the alkoxylated triazine-arylhydroxy-aldehyde condensate. Such additive materials include, but are not limited to, surfactants, blowing agents, cell openers, fillers, pigments and/or colorants, drying agents, reinforcing agents, biocides, preservatives, antioxidants, flame retardants, and combinations thereof. The additive material may contain about 0 wt. of the formulation or reaction mixture. To about 20 wt%, such as about 4 wt. To about 16 wt%, for example about 11 wt. To about 13 wt%.

When a flame retardant is included, the flame retardant may be a phosphorus-containing flame retardant. Examples of phosphorus-containing flame retardants include triethyl phosphate (TEP), triphenyl phosphate (TPP), trischloropropyl phosphate (TCPP), dimethylpropane phosphate, resorcinol bis (diphenyl phosphate) (RDP), bisphenol A diphenyl. Phosphate (BADP), and tricresyl phosphate (TCP), dimethyl methylphosphonate (DMMP), diphenyl cresyl phosphate and aluminum diethyl phosphinate.

The relative amounts of the polyisocyanate and the alkoxylated triazine-arylhydroxy-aldehyde condensate are selected to produce the polymer. The ratio of these components is generally referred to as the'isocyanate index' meaning the ratio of isocyanate groups to isocyanate-reactive groups provided by the alkoxylated triazine-arylhydroxy-aldehyde condensate multiplied by 100. The isocyanate index is generally at least 50 and may be up to 1000 or more, such as from about 50 to about 900. Rigid polymers, such as structural polyurethanes and rigid foams, are generally made using an isocyanate index of 90 to 200. When flexible or semi-flexible polymers are prepared, the isocyanate index is generally between 70 and 125. Polymers containing isocyanurate groups are often made with an isocyanate index of at least 150, up to 600 or more.

To form the polymer, the polyisocyanate compound and the alkoxylated triazine-arylhydroxy-aldehyde condensate are mixed and cured. The curing step is accomplished by treating the reaction mixture under conditions sufficient to cause the polyisocyanate compound and the alkoxylated triazine-arylhydroxy-aldehyde condensate to react to form the polymer.

One example is mixing the alkoxylated triazine-arylhydroxy-aldehyde condensate with pMDI for 10 seconds at ambient conditions to create a reaction between the hydroxyl group and the isocyanate. This reaction generates heat and can produce either a rigid foam or a flexible foam depending on the length of the alkoxylation.

According to the present invention, a wide variety of polymers can be prepared through the presence of certain alkoxylated-triazine-arylhydroxy-aldehyde condensates, certain polyisocyanates, the optional substances described below, and the appropriate selection of reaction conditions. have. The method of the present invention comprises various types of polyurethane and/or polyisocyanurate polymers, such as rigid polyurethane foams, sealants and adhesives (e.g., moisture-curable types), hot-melt powders, wood binders, cast elastomers, Flexible or semi-flexible reactive injection molded parts, rigid structural composites, flexible polyurethane foams, binders, cushioning and/or integral backings for carpets and other textiles, semi-flexible foams, pipe insulation, automotive cavity sealing, automotive noise and /Or vibration damping materials, microcellular foams such as shoe soles, tire fillers and the like. These polymers can then be used to make articles.

The novel polymers produced herein may be applied as part of the polymer production process, eg, to a substrate at the point of use, or may be applied after complete polymer production for use in a later application process. Suitable substrates may include inorganic materials such as silica or metal, or organic materials such as wood or plastic, or combinations thereof. Examples of suitable substrates include, among others, proppant and proppant substrates, wood, building materials and structural surfaces.

[Example]

In this example, the triazine-arylhydroxy-aldehyde condensation composition was prepared using the method described in U.S. Patent No. 9,249,251, which document is incorporated herein by reference to the extent not contradictory with the present invention. .

The following method was used in Examples 1 to 6, and the data are reported in Tables 1 and 2.

Water % : The percentage of water remaining in the product after alkoxylation was determined by standard Karl Fischer titration using a Karl Fischer titrator similar to ASTM D6304.

Hydroxyl value : This value was obtained using a titration method as specified in the American Oil Chemists' Society (AOCS) CD 13-60 method.

5% water solubility : This was determined by mixing 5 g of the material of Examples 1 to 6 with 95 g of distilled water for 30 minutes and checking the visual appearance of the system. If the system was clear and no precipitate appeared, it would be considered soluble, and if the system exhibited any turbidity, haze or precipitate, it was considered insoluble.

Viscosity at 30° C.: The viscosity of the material was measured from a parallel plate Rheometer operated in a rotating manner under a scanning shear rate of 0.1 to 100 l/s at 30° C. The viscosity of the material, extrapolated to zero shear viscocity, was reported in mPa·s.

pH (IPA/5% in water) : The material was dissolved in 50% isopropanol (IPA) aqueous solution and the pH of the entire system was read using a calibrated pH probe to determine the pH.

Control

The triazine-arylhydroxy-aldehyde condensate control sample was prepared according to the method of US Patent No. 9,249,251. It is partially briefly described as follows. 546.0 g of phenol (5.8 mol), 1.1 g of benzoic acid and 79.1 g of melamine (0.63 mol) were charged to a reaction vessel to form a reaction mixture. The reaction mixture was heated to 80° C. and 55.8 g of formaldehyde was added over 40 minutes in the form of a 50% aqueous solution. After addition, the reaction was distilled at atmospheric pressure to 123°C and maintained at 123°C for 2 hours. Then, the reaction mixture was cooled to 80° C., and 37.2 g of aqueous formaldehyde in the form of 50% aqueous solution was added over 30 minutes, followed by atmospheric distillation to 123° C. and maintained at 123° C. for 2 hours. The reaction mixture was then further subjected to atmospheric pressure distillation to 165° C., followed by progressive vacuum distillation to 27 inches of mercury over 3 hours while maintaining 165° C., and then heated to 175° C. while maintaining 27 inches of mercury. The reaction mixture was held at 175[deg.] C. for 1 hour and then steam sparged for 60 minutes under vacuum distillation. A total of 426.6 g of distillate was removed and 212.9 g of arylhydroxy-aldehyde condensate was discharged from the reaction vessel, showing brittle and solid-like properties upon cooling.

Example 1

500 g of the triazine-arylhydroxy-aldehyde condensate formed from the control example and 50% potassium hydroxide in methanol were charged to a 2 L pressure reactor equipped with a mechanical stirrer, a reflux condenser, a thermocouple and a thermocouple controlled heating mantle. The reactor was flushed with nitrogen to remove air, heated to 90° C., and vacuum dehydrated at 120° C. to remove trace amounts of water and methanol. The mixture was then heated to a temperature of 150-160°C. Then, 20% of 1015 g ethylene oxide was charged to the flask to start the reaction, and then the remaining ethylene oxide was added to a pressure ^{of 4.0 kg/cm 2.} The reaction mixture was reacted at 165° C. at 4.0 kg/cm ² , then cooled to 70-75° C. and neutralized to pH 7-8. The yield was 87%.

Example 2

500 g of the triazine-arylhydroxy-aldehyde condensate formed from the control example and 50% potassium hydroxide in methanol were charged to a 3 L pressure reactor equipped with a mechanical stirrer, a reflux condenser, a thermocouple and a thermocouple controlled heating mantle. The reactor was flushed with nitrogen to remove air, heated to 90° C., and vacuum dehydrated at 120° C. to remove trace amounts of water and methanol. The mixture was then heated to a temperature of 150-160°C. Then, 20% of 3254 g ethylene oxide was charged to the flask to start the reaction, and then the remaining ethylene oxide was added to a pressure ^{of 4.0 kg/cm 2.} The reaction mixture was reacted at 165° C. at 4.0 kg/cm ² , then cooled to 70-75° C. and neutralized to pH 7-8. The yield was 85%.

Example 3

135 g of the triazine-arylhydroxy-aldehyde condensate formed from the control example and 50% potassium hydroxide in methanol were charged into a 2 L pressure reactor equipped with a mechanical stirrer, a reflux condenser, a thermocouple and a thermocouple controlled heating mantle. The reactor was flushed with nitrogen to remove air, heated to 90° C., and vacuum dehydrated at 120° C. to remove trace amounts of water and methanol. The mixture was then heated to a temperature of 150-160°C. Then, 20% of 1370 g ethylene oxide was charged into the flask to start the reaction, and then the remaining ethylene oxide was added to a pressure ^{of 4.0 kg/cm 2.} The reaction mixture was reacted at 165° C. at 4.0 kg/cm ² , then cooled to 70-75° C. and neutralized to pH 7-8. The yield was 92%.

The compositions of Examples 1 to 3 were tested for physical properties. The results are shown in Table 1: Physical properties of triazine-arylhydroxy-aldehyde condensates alkoxylated with ethylene oxide.

Table 1 demonstrates the properties of the alkoxylated triazine-arylhydroxy-aldehyde condensate after alkoxylation and shows a control before alkoxylation. These properties, in particular viscosity, hydroxyl value, water percent, and pH are important for the application of alkoxylated triazine-arylhydroxy-aldehyde condensates in the preparation of polyurethane foams. The water solubility indicates whether the resulting alkoxylated triazine-arylhydroxy-aldehyde condensate is hydrophilic or hydrophobic. The condensate of Example 3 is soluble in water and is hydrophilic or miscible with water, and the condensate of Examples 1 and 2 is hydrophobic because it is insoluble. The above examples also suggest that increasing the length of alkoxylation with ethylene oxide increases the water solubility until a water-soluble product is formed corresponding to the more hydrophilic condensate.

In addition, the alkoxylation produces a material that is liquid at 30° C. and allows its use in liquid polyurethane applications such as applying heat or mixing with other polyols that require special handling conditions. Finally, the hydroxyl number of the control sample is very high, 739 mg KOH/g, which requires a high amount of isocyanate to maintain the overall isocyanate index of the polyurethane foam, while 150-400 mg KOH/ The hydroxyl value in the g range is more suitable for most polyurethane foam applications.

Example 4

408 g of the triazine-arylhydroxy-aldehyde condensate formed from the control example and 50% potassium hydroxide in methanol were charged to a 2 L pressure reactor equipped with a mechanical stirrer, a reflux condenser, a thermocouple and a thermocouple controlled heating mantle. The reactor was flushed with nitrogen to remove air, heated to 90° C., and vacuum dehydrated at 120° C. to remove trace amounts of water and methanol. The mixture was then heated to a temperature of 150-160°C. Then, 20% of 1092 g propylene oxide was charged to the flask to start the reaction, and then the remaining propylene oxide was added to a pressure ^{of 4.0 kg/cm 2.} The reaction mixture was reacted at 165° C. at 4.0 kg/cm ² , then cooled to 70-75° C. and neutralized to pH 7-8. The isolated yield was 48%.

Example 5

185 g of the triazine-arylhydroxy-aldehyde condensate formed from the control example and 50% potassium hydroxide in methanol were charged to a 2 L pressure reactor equipped with a mechanical stirrer, a reflux condenser, a thermocouple and a thermocouple controlled heating mantle. The reactor was flushed with nitrogen to remove air, heated to 90° C., and vacuum dehydrated at 120° C. to remove trace amounts of water and methanol. The mixture was then heated to a temperature of 150-160°C. Then, 20% of 1316 g propylene oxide was charged to the flask to start the reaction, and then the remaining propylene oxide was added to a pressure ^{of 4.0 kg/cm 2.} The reaction mixture was reacted at 165° C. at 4.0 kg/cm ² , then cooled to 70-75° C. and neutralized to pH 7-8. The isolated yield was 86%.

Example 6

105 g of the triazine-arylhydroxy-aldehyde condensate formed from the control example and 50% potassium hydroxide in methanol were charged to a 2 L pressure reactor equipped with a mechanical stirrer, a reflux condenser, a thermocouple and a thermocouple controlled heating mantle. The reactor was flushed with nitrogen to remove air, heated to 90° C., and vacuum dehydrated at 120° C. to remove trace amounts of water and methanol. Then the mixture was heated to a temperature of 150-160°C. Then, 20% of 1405 g propylene oxide was charged to the flask to start the reaction, and then the remaining propylene oxide was added to a pressure ^{of 4.0 kg/cm 2.} The reaction mixture was reacted at 165° C. at 4.0 kg/cm ² , then cooled to 70-75° C. and neutralized to pH 7-8. The yield was 89%.

The compositions of Examples 4-6 were tested for physical properties. The results are shown in Table 2: Physical properties of triazine-arylhydroxy-aldehyde condensates alkoxylated with propylene oxide.

Table 2 demonstrates the properties of the alkoxylated triazine-arylhydroxy-aldehyde condensate after alkoxylation with propylene oxide and compares the results for the control group of the triazine-arylhydroxy aldehyde condensation. These properties, in particular viscosity, hydroxyl value, water percent, and pH are important for the application of alkoxylated triazine-arylhydroxy-aldehyde condensates in the preparation of polyurethane foams. The water solubility was used as an indicator of whether the resulting alkoxylated triazine-arylhydroxy-aldehyde condensate was hydrophilic or hydrophobic, and the alkoxylated triazine-arylhydroxy-aldehyde condensation prepared by propylene oxide It can be seen that all of the water is hydrophobic and insoluble in water even with a long propoxylation length, as shown in Example 6.

Example 7: Viscosity of alkoxylated triazine-arylhydroxy-aldehyde condensate

An ARES-G2 rheometer (TA Instruments) equipped with a stainless steel parallel plate was operated under rotation mode to determine the viscosities of Examples 1 to 6 at 25°C, 30°C, 35°C and 40°C. The viscosity was determined from the "zero-shear" approximation where the viscosity was measured as a function of shear rate (0.1-100 l/s). The zero shear viscosity was determined by extrapolating the viscosity curve to zero shear, taking into account non-Newtonian behavior at low shear rates such as shear thinning. Due to the zero-shear approximation, the viscosity appears to be higher than that reported within the Newtonian region of the viscosity curve. Ten data points were measured for every magnitude change in shear rate, such as ten points between 0.1 and 1 l/s. If the material exhibited a non-Newtonian behavior such as shear thinning, it was determined at a lower temperature. The results are shown in Tables 3a-3b: Condensate Viscosity Results for Examples 1-6 below. An example showing shear thinning is denoted by (ST).

Tables 3a and 3b show the temperature dependence of viscosity for the various alkoxylated triazine-arylhydroxy-aldehyde condensates. The temperature has a significant effect on the viscosity of the product and sometimes a temperature change of 5°C is 40% for Newtonian alkoxylated triazine-arylhydroxy-aldehyde condensates, and non-Newtonian alkoxylated triazine-arylhydroxy- In the case of aldehyde condensates, the viscosity is reduced by 93%. This data is important for polyurethane formulators as the viscosity of each component of the polyurethane system can have a significant impact on the overall properties of the final system.

Based on the results of Tables 1 to 4, alkoxylated triazine-arylhydroxy-aldehyde condensates can be used as rheology modifiers for polyurethane crosslinking agents to further adjust the viscosity of the polyurethane system.

Example 8 (polyurethane)

8.85 g of the alkoxylated triazine-arylhydroxy-aldehyde condensate having an average repeating unit of 3 ethylene oxide units was mixed with 10 g of pMDI for 20 seconds using a metal spatula. The mixture showed exotherm within 20 seconds. This material exhibited some foaming properties due to residual moisture, cured, and was not tacky after 30 seconds. The final material was an intratable solid material with a rigid, foam-like structure.

Example 9

5.0 g of the alkoxylated triazine-arylhydroxy-aldehyde condensate having an average repeating unit of 8 ethylene oxide units was mixed with 10 g of pMDI for 10 seconds using a metal spatula. The mixture showed exotherm within 10 seconds. This material exhibited some foaming properties due to residual moisture, cured, and was not tacky after 30 seconds. The final material was a difficult-to-process material with some flexibility and foam-like structure.

Example 10

3.8 g of the alkoxylated triazine-arylhydroxy-aldehyde condensate having an average repeating unit of 15 ethylene oxide units was mixed with 10 g of pMDI for 10 seconds using a metal spatula. The mixture showed exotherm within 15 seconds. This material exhibited some foaming properties due to residual moisture, and was not tacky after 30 seconds. The material was a flexible foam, especially at room temperature.

Example 11

A 5 mg sample was cut from the material resulting from Example 9 and placed in a hermetically sealed differential scanning calorimetry pan. The sample was exposed to a heating/cooling/heating cycle from -50°C to 180°C at a ramping rate of 10°C/min and rapid cooling without control to -50°C in the cooling cycle. The first heating cycle demonstrated that the material exhibited a fair cure and had a maximum exothermic temperature at 95° C. and a total heat of enthalpy of 23.7 J/g. The glass transition temperature from the first heating scan was 14°C and in the second heating scan it was 34°C.

Example 12

A 5 mg sample was cut from the material resulting from Example 10 and placed in a hermetically sealed differential scanning calorimetry pan. The sample was exposed to a heating/cooling/heating cycle from -50°C to 180°C at a temperature control rate of 10°C/min and rapid cooling without control to -50°C in the cooling cycle. The first heating cycle demonstrated that the material showed complete cure and did not exhibit an exothermic transition. The glass transition temperatures from the two heating scans were 9.8°C and 10°C.

Example 13

A 5 mg sample was cut from the material resulting from Example 11 and placed in a hermetically sealed differential scanning calorimetry pan. The sample was exposed to a heating/cooling/heating cycle from -80°C to 180°C at a temperature control rate of 10°C/min and rapid cooling without control to -50°C in the cooling cycle. The first heating cycle demonstrated that the material showed complete cure and did not exhibit an exothermic transition. The glass transition temperatures from the two heating scans were -38°C and -37°C.

Thermogravimetric analysis method

A 10 mg sample was cut from the material produced in Examples 9, 10, or 11, placed in an alumina thermogravimetric crucible, and heated from room temperature to 1000°C. The onset of decomposition was characterized by the peak decomposition temperature and weight loss of _{5% (T d5%} ) and 10% (T _d10% ), calculated from the derivative (%/°C) of the weight curve. The results are reported in Table 4: Thermogravimetric Analysis Results.

Table 4 suggests that the onset of decomposition of the polyurethanes prepared from Examples 11, 12 and 13 exhibit different thermal stability. The onset of decomposition was determined by weight loss of _{5% (T d5%} ) and 10% (T _d10%). Example 13 showed the highest thermal stability with _{a T d5%} of 262°C and a T _{d10% of 314°C.} The polyurethane of Example 13 exhibited about 6% higher thermal stability than Example 12 and 18% higher thermal stability than Example 11. This suggests that the length of ethoxylation plays an important role in the thermal stability of the final polyurethane polymer.

Foam manufacturing method

Foam was prepared using a high-torque mixer (CRAFSTMAN 10-Inch Drill Press, model number 137.219000) at a speed of 3,100 rpm. The polyol component and isocyanate component of the foam system were mixed for 5 seconds. Thereafter, the mixture was transferred to an open cake box before the cream time and raised. Foam was prepared by transferring the foaming mixture into a cake box with dimensions of 9"x9"x5". Using the foam, cream time, gel time, rise time, tack-free time, density, and cell structure The visual appearance of was evaluated.

For Examples 14-20, Lupranate M20S is a polymeric methylene diphenyl diisocyanate (pMDI) available from BASF Corporation.

Example 14

Polyurethane foam reacts according to the method of the present application, Lupranate M20S (A side), a polymeric methylene diphenyl diisocyanate having an isocyanate index of 110, and a polyol component (B side) prepared from the corresponding components in Table 5 Was prepared. The mixing time was kept constant, and the cream time, gel time, rise time, and tack-free time were all measured after pouring the mixture into a polyethylene lined cardboard box. The resulting foam had a density of 29.52 kg per cubic meter and had a uniform and coarse cell structure.

Example 15

Polyurethane foam reacts according to the method of the present application, Lupranate M20S (A side), a polymeric methylene diphenyl diisocyanate having an isocyanate index of 110, and a polyol component (B side) prepared from the corresponding components in Table 5 Was prepared. The mixing time was kept constant, and the cream time, gel time, rise time, and tack-free time were all measured after pouring the mixture into a polyethylene internalized cardboard box. The resulting foam had a density of 30.69 kg per cubic meter and had a uniform and fine cell structure.

Example 16

Polyurethane foam reacts according to the method of the present application, Lupranate M20S (A side), a polymeric methylene diphenyl diisocyanate having an isocyanate index of 110, and a polyol component (B side) prepared from the corresponding components in Table 5 Was prepared. The mixing time was kept constant, and the cream time, gel time, rise time, and tack-free time were all measured after pouring the mixture into a polyethylene internalized cardboard box. The resulting foam had a density of 28.45 kg per cubic meter and had a uniform, slightly coarse cell structure.

Example 17

Polyurethane foam reacts according to the method of the present application, Lupranate M20S (A side), a polymeric methylene diphenyl diisocyanate having an isocyanate index of 110, and a polyol component (B side) prepared from the corresponding components in Table 5 Was prepared. The mixing time was kept constant, and the cream time, gel time, rise time, and tack-free time were all measured after pouring the mixture into a polyethylene internalized cardboard box. The resulting foam had a density of 30.23 kg per cubic meter and had a uniform and fine cell structure.

Example 18

Polyurethane foam reacts according to the method of the present application, Lupranate M20S (A side), a polymeric methylene diphenyl diisocyanate having an isocyanate index of 110, and a polyol component (B side) prepared from the corresponding components in Table 5 Was prepared. The mixing time was kept constant, and the cream time, gel time, rise time, and tack-free time were all measured after pouring the mixture into a polyethylene internalized cardboard box. The resulting foam had a density of 37.25 kg per cubic meter and had a very fine cell structure.

Example 19

Polyurethane foam reacts according to the method of the present application, Lupranate M20S (A side), a polymeric methylene diphenyl diisocyanate having an isocyanate index of 110, and a polyol component (B side) prepared from the corresponding components in Table 5 Was prepared. The mixing time was kept constant, and the cream time, gel time, rise time, and tack-free time were all measured after pouring the mixture into a polyethylene internalized cardboard box. The resulting foam had a density of 28.90 kg per cubic meter and had a fine cell structure.

Example 20

Polyurethane foam reacts according to the method of the present application, Lupranate M20S (A side), a polymeric methylene diphenyl diisocyanate having an isocyanate index of 110, and a polyol component (B side) prepared from the corresponding components in Table 5 Was prepared. There is no catalyst in the formulation of Example 20. The mixing time was kept constant, and the cream time, gel time, rise time, and tack-free time were all measured after pouring the mixture into a polyethylene internalized cardboard box. The resulting foam had a density of 42.36 kg per cubic meter.

Table 5: In the polyol B side formulation of Examples 14 to 20, the substances and amounts are as follows:

Terol 250 is an aromatic polyester polyol commercially available from Huntsman Corporation. Jeffol R-470X is a Mannich polyol commercially available from Huntsman Corporation. Poly-G 74-376 is a sucrose-initiating polyether polyol prepared from ethylene oxide and propylene oxide commercially available from Monument Chemical.

Polycat 8 is a low molecular weight amine catalyst commercially available from Air Products and Chemicals, Inc. Pelcat 9540-A is a potassium salt catalyst of octanoic acid commercially available from Ele Corporation.

The diluent DBE ester is a mixture of dibasic esters of methyl and ethyl esters of adipic acid, succinic acid and glutaric acid available from Invista, Inc. CO-28B is a cell opener commercially available from Ventrex Chemical. Dow Corning 193 is a silicone surfactant commercially available from Dow Corning. Solistice LBA is a hydrofluorinated olefin blowing agent commercially available from Honeywell Inc.

The alkoxylated triazine-arylhydroxy-aldehyde (ATAHA) condensate of Table 5 was prepared by the following procedure. 1000 g of triazine-arylhydroxy-aldehyde condensate, 50 g of glycerol, 6.6 g of potassium hydroxide dissolved in 13.3 g of methanol, 5 L pressure reactor equipped with a mechanical stirrer, reflux condenser, thermocouple and thermocouple controlled heating mantle Was charged to. The reactor was flushed with nitrogen to remove air, heated to 90° C., and vacuum dehydrated at 120° C. to remove trace amounts of water and methanol. The mixture was then heated to a temperature of 140-150°C. Then, 59.25 g of propylene oxide was charged into the vessel and reacted, and the reaction mixture was heated to a temperature of 155-160°C. Then, 2200 g of ethylene oxide was added to a pressure ^{of 3.5 to 4.0 kg/cm 2.} After completion, the reaction mixture was cooled to 70-75[deg.] C. and neutralized with 16 g of salicylic acid. The yield was 95%, and the material had a viscosity of 12400 mPa·s at 30° C., an OH# of 364 mg KOH/g, and a moisture content of 0.3%.

Table 5 shows several formulation modifications using the alkoxylated-triazine-arylhydroxy-aldehyde condensate prepared from Example 1, and Example 16 shows the alkoxylated triazine-arylhydroxy-aldehyde condensate. No control formulation is shown. The resulting polyurethane foam reactivity properties are shown in Table 6. The method of measuring the reactivity of Table 6 was performed according to ASTM D7487-13e1. Examples 15, 18 and 20 are free of Mannich (base) polyols. There is no catalyst in Example 20.

The resulting polyurethane foam reactivity properties are shown in Table 6. Table 6: The method of measuring the reactivity in the reactivity of the polyurethane foam examples was carried out according to ASTM D7487-13e1.

The reactivity of the foam formulation is evaluated based on the time it takes to achieve the cream, gel, rise and tack state. The less time it takes to achieve this state, the faster the formulation will be responsive. In Table 6, Example 18, containing the maximum concentration of alkoxylated triazine-arylhydroxy-aldehyde condensate, exhibited the highest reactivity among all the polyurethane foams produced and was significantly faster than the control Example 16. Examples 14 and 18 directly compare the reactivity between Mannich polyols to alkoxylated triazine-arylhydroxy-aldehyde condensates.

It is clear that the alkoxylated triazine-arylhydroxy-aldehyde condensate is significantly more reactive than Mannich polyols. In addition, Examples 16, 19, 15 and 18 illustrate the effect of increasing the concentration of the alkoxylated triazine-arylhydroxy-aldehyde condensate. In the above embodiments, as the concentration of the alkoxylated triazine-arylhydroxy-aldehyde condensate increases from 0% to 10%, 15%, and 30%, respectively, the reactivity is also cream, gel, rise and no tack. It increases continuously as indicated by the decrease in time.

Thus, the data in Table 5 demonstrates the significantly higher reactivity of the alkoxylated triazine-arylhydroxy-aldehyde condensate compared to the reference polyol. This table also shows that the use of the novel polyols of the present invention can minimize the use of Mannich (base) polyols or low molecular amine catalysts, which can cause a myriad of health problems in humans, including green blindness and respiratory irritation, or in the above formulations. Show that you can do it.

In addition, due to the high functional group and aromaticity of the alkoxylated triazine-arylhydroxy-aldehyde condensate, the formulator will be able to develop a polyurethane composition free of catalysts and additional polyols, which simplifies complex formulations and Errors in producing side formulations can be minimized. One example of this formulation may be an alkoxylated triazine-arylhydroxy-aldehyde condensate, suitable surfactants, suitable blowing agents and suitable flame retardants.

Data on flame retardancy are provided in Table 7: Flame properties of Examples 14-19 below.

Burn rate and mass retention after combustion were measured using a self-modified ASTM D 4986 flammability test. In the in-house test, a Bernzomatic torch TS4000 was used. This flammability test is relatively straightforward and is designed to allow relative comparisons between different foam types. Lower mm/speed and higher mass retention indicate good response to fire or improved fire resistance.

Table 7 shows the effect of polyols on the response of the foam to fire. As the concentration of the alkoxylated triazine-arylhydroxy-aldehyde condensate increased from 0% to 10%, 15%, and 30% in Examples 16, 19, 15 and 18, respectively, the combustion rate was continuously decreased. And, at a maximum concentration of 30%, the foam exhibited self-extinguishing properties in the absence of both sugar-based polyethers and Mannich polyols. The higher mass retention of the residue is also a direct result of improved flame retardancy. Example 16, the control sample, had a mass retention of 45%; Example 18 with 30% alkoxylated triazine-arylhydroxy-aldehyde condensate had a mass retention of 87%.

In addition to allowing a simplified B-side formulation, also the alkoxylated triazine-arylhydroxy-aldehyde condensate may be a sucrose polyether polyol or other polyether with sufficient hydrophilicity, a Mannich polyol, an aromatic polyester. Compared to common polyols such as polyols, ethylene diamine polyether polyols, superior mixing with blowing agents such as pentane and related isomers, hydroxyl fluorinated olefins, hydroxyl fluorinated hydrocarbons, and other halogenated blowing agents, and aromatic isocyanates It is predicted to have Mars.

Finally, the alkoxylated triazine-arylhydroxy-aldehyde condensate when reacted with isocyanate demonstrated a relatively high onset of thermal decomposition, and due to the nitrogen content present in the polyol, a synergistic effect with phosphorus-containing compounds Can be produced, which could significantly improve the flame retardant properties of a typical polyurethane foam or related article.

While the present invention has been described and illustrated with reference to specific embodiments, one of ordinary skill in the art will understand that the present invention is suitable for variations that are not necessarily illustrated herein.

Claims (14)

Polyisocyanate; And
Isocyanate-reactive compounds comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate
A polymer prepared using a formulation containing. The polymer of claim 1, wherein the formulation is free of catalysts, flame retardants, Mannich polyols, or combinations thereof. The polymer of claim 1, wherein the formulation comprises monomers of polyisocyanate and alkoxylated triazine-arylhydroxy-aldehyde. The polymer of claim 3, wherein the polyisocyanate comprises methylene diphenyl diisocyanate and the alkoxylated triazine-arylhydroxy-aldehyde comprises ethoxylated triazine-phenol-formaldehyde. The polymer of claim 1, wherein the polymer is a polyurethane foam, a wood binder, or a combination thereof. The polymer of claim 1, wherein the formulation further comprises a phosphorus-containing flame retardant, diluent, catalyst, or combinations thereof. The polymer of claim 1, wherein the polyisocyanate is a blocked isocyanate. The polymer of claim 1, wherein the polyisocyanate comprises a diisocyanate. An article made from the polymer of claim 1. Forming a reaction mixture comprising;
Polyisocyanate, and
Isocyanate-reactive compounds comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate; And,
Curing the reaction mixture to form a polymer
How to include. 11. The method of claim 10, further comprising applying the polymer to a substrate. 11. The method of claim 10, wherein the substrate comprises an inorganic material or an organic material. The method of claim 10, wherein the reaction mixture is free of catalysts, flame retardants, Mannich polyols, or combinations thereof. The method of claim 10, wherein the reaction mixture further comprises a phosphorus-containing flame retardant, diluent, catalyst, or combinations thereof.