阅读说明：本技术 用于生产烷氧基化的三嗪-芳基羟基-醛缩合物的新组合物和方法 (Novel compositions and methods for producing alkoxylated triazine-arylhydroxy-aldehyde condensates ) 是由 G·S·维斯瓦纳坦 A·马约拉纳 S·施罗特 P·库卡拉 于 2019-07-19 设计创作，主要内容包括：本文所述的实施方案通常涉及三嗪-芳基羟基-醛缩合物的方法和化学组合物。在一种实施方案中,三嗪-芳基羟基-醛缩合物与烷氧基化剂反应来形成烷氧基化的三嗪-芳基羟基-醛缩合物。(Embodiments described herein generally relate to methods and chemical compositions of triazine-arylhydroxy-aldehyde condensates. In one embodiment, the triazine-arylhydroxy-aldehyde condensate is reacted with an alkoxylating agent to form an alkoxylated triazine-arylhydroxy-aldehyde condensate.)

1. A condensation product of a reaction mixture comprising:

triazine-arylhydroxy-aldehyde condensates; and

an alkoxylating agent comprising:

an alkylene oxide; and

optionally an alkylene carbonate; and

optionally a catalyst.

2. The condensation product according to claim 1, wherein the at least one alkylene oxide comprises a compound selected from the group consisting of: ethylene oxide, propylene oxide, butylene oxide, and combinations thereof.

3. The condensation product according to claim 1, wherein the optional alkylene carbonate comprises a compound selected from the group consisting of: ethylene carbonate, propylene carbonate, butylene carbonate, and combinations thereof.

4. The condensation product according to claim 1, wherein the optional catalyst comprises a compound selected from the group consisting of: metal hydroxides, metal carbonates, tertiary amines, phosphines, transition metal bases, metal phosphates, organic acids, and combinations thereof.

5. Condensation product according to claim 1, wherein the triazine-arylhydroxy-aldehyde condensation product has from 1mol to 20mol of alkoxylating agent per reaction site.

6. The condensation product according to claim 1, wherein the condensation product comprises an alkoxylated triazine-arylhydroxy-aldehyde condensate having the structure:

wherein R is₆Is of formula II or formula III, and wherein R₇Is a hydrogen atom, formula II or formula IV;

wherein R is₈And R₉Each 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)₂NH (formula II), -N (formula II) (formula IV), -N (formula II)₂NH (formula III), -N (formula III) (formula IV), -N (formula III)₂NH (formula V), -N (formula IV) (formula V), -N (formula V)₂or-NH₂；

Wherein R is₁And R₂Each independently is 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 and containing a hydroxyl group;

wherein R is₁₀Is hydrogen atom, alkyl group having 1 to 10 carbon atoms and containing hydroxyl group, phenyl group, vinyl group, propenyl group, phenyl group containing hydroxyl group, pyrrolyl group or furyl group;

wherein R is₁₁And R₁₂Each independently is 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 hydroxyphenyl group, or an alkyl group having 1 to 10 carbon atoms and at least one carbon substituted with i) a hydroxyl group, ii) a hydroxyphenyl group, or iii) a phenyl group;

or wherein R is₁₁And R₁₂Combine to form a common aromatic ring with or without a hydroxyl group;

wherein R is₁₃And R₁₄Each independently is 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)₂NH (formula V), -N ((formula IV) (formula V)), -N (formula V)₂or-NH₂；

Wherein R is₁₅、R₁₆And R₁₇Each independently is 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)₂NH (formula V), -N (formula IV) (formula V), -N (formula V)₂or-NH₂；

Wherein each m is independently 1-10, each n is independently 0-10,

wherein each x is independently 1 to 20 and each x ' is independently 1 to 20 when the alkoxylating agent is an alkylene oxide, or wherein each x is independently 1 to 20 and each x ' is independently 1 to 20 when the alkoxylating agent is a combination of an alkylene oxide and an alkylene carbonate, and the average of all x and x ' is greater than 2,

and wherein the monomers indicated by m and n are arranged in any order, combination or subcombination.

7. The condensation product according to claim 1, wherein the condensation product comprises one or more compounds selected from the group consisting of:

and combinations thereof.

8. The condensation product according to claim 1, wherein the condensation product comprises a nitrogen content of about 1 wt% to 41 wt%.

9. The condensation product according to claim 1, wherein the condensation product comprises an aromatic content of about 1 to 69 weight percent.

10. The condensation product according to claim 1, wherein the condensation product comprises a viscosity at 25 ℃ in the range of 0.01 pascal seconds to 30 pascal seconds.

11. An alkoxylated triazine-arylhydroxy-aldehyde condensate compound having the structure:

wherein R is₆Is of formula II or formula III, and wherein R₇Is a hydrogen atom, formula II or formula IV;

wherein R is₈And R₉Each independently is 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)₂NH (formula II), -N (formula II) (formula IV), -N (formula II)₂NH (formula III), -N (formula III) (formula IV), -N (formula III)₂NH (formula V), -N (formula IV) (formula V), -N (formula V)₂or-NH₂；

Wherein R is₁And R₂Each independently is 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 and containing a hydroxyl group;

wherein R is₁₀Is hydrogen atom, alkyl group having 1 to 10 carbon atoms and containing hydroxyl group, phenyl group, vinyl group, propenyl group, phenyl group containing hydroxyl group, pyrrolyl group or furyl group;

wherein R is₁₁And R₁₂Each independently is 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 hydroxyphenyl group, or an alkyl group having 1 to 10 carbon atoms and at least one carbon substituted with i) a hydroxyl group, ii) a hydroxyphenyl group, or iii) a phenyl group;

or wherein R is₁₁And R₁₂Combine to form a common aromatic ring with or without a hydroxyl group;

wherein R is₁₃And R₁₄Each independently is 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)₂NH (formula V), -N ((formula IV) (formula V)), -N (formula V)₂or-NH₂；

Wherein R is₁₅、R₁₆And R₁₇Each independently is 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)₂NH (formula V), -N (formula IV) (formula V), -N (formula V)₂or-NH₂；

Wherein each m is independently 1-10, each n is independently 0-10,

wherein each x is independently 1 to 20 and each x ' is independently 1 to 20 when the alkoxylating agent is an alkylene oxide, or wherein each x is independently 1 to 20 and each x ' is independently 1 to 20 when the alkoxylating agent is a combination of an alkylene oxide and an alkylene carbonate, and the average of all x and x ' is greater than 2,

and wherein the monomers represented by m and n are arranged in any order, combination, or subcombination.

12. The compound according to claim 11, wherein the alkoxylated triazine-arylhydroxy-aldehyde condensate composition comprises one or more compounds selected from the group consisting of compounds having the following structures:

13. the compound according to claim 11, wherein the alkoxylated-triazine-arylhydroxy-aldehyde condensate composition further comprises a rheology modifier in polyurethane crosslinking applications.

14. A method, comprising:

reacting a 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

forming an alkoxylated triazine-arylhydroxy-aldehyde condensate composition.

15. The process of claim 14, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, and in any order.

16. The process of claim 14 wherein the alkoxylating agent can be alkylene oxide and alkylene carbonate such as ethylene oxide, propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate and mixtures thereof.

17. The process according to claim 14, wherein the manufacture of the triazine-arylhydroxy-aldehyde condensate and the formation of the alkoxylated triazine-arylhydroxy-aldehyde condensate composition can be carried out in the same reactor.

18. The process of claim 14, wherein making the triazine-arylhydroxy-aldehyde condensate and forming the alkoxylated triazine-arylhydroxy-aldehyde condensate composition can be carried out in a continuous, semi-continuous, or semi-continuous, semi-continuous to batch, or batch-type reactor.

Technical Field

The present invention relates to alkoxylated triazine-arylhydroxy-aldehyde condensate compositions and methods of making these compositions.

Background

Polyurethane is one of the most common classes of polymeric materials. They are particularly useful in rigid and flexible foams. Flexible polyurethane foams are used as cushioning for a variety of consumer and commercial products, including mattresses, furniture, automotive interiors, carpet underlayments and packaging. Rigid polyurethane and polyisocyanurate (polyisocyanurate) foams produce one of the most popular, energy efficient and versatile insulators worldwide. Environmental health and safety as well as fire resistance are driving changes in the insulation industry. The high thermal insulation of rigid polyurethanes makes them the most suitable and effective technology to address these needs. These global trends drive the need for continued innovation throughout the polyurethane industry.

Polyurethane foams are produced by reacting isocyanates with polyols. The polyol component is typically one or more polyols, along with surfactants, catalysts, flame retardants, and blowing agents to produce a foam. The most common polyols used in the industry are polyether polyols and polyester polyols. Each of these classes of compounds has their own advantages and disadvantages. Polyether polyols provide hydrolytic stability, lower viscosity and flexibility. Aromatic polyesters are known to contribute to flame retardancy and higher modulus. However, they are typically limited in functionality and are inherently more viscous and therefore the formulations, especially in rigid PU systems, have to use co-polyols such as polyether polyols with higher functionality. Furthermore, the sugar-based polyols, one of the most commonly used co-polyols in these formulations, do not provide any flame retardancy.

It has been found that alkoxylated phenol-aldehyde resins can be used to prepare a variety of polymer products, including polyurethane compositions and foamed products. These are typically referred to as novolak-based polyether polyols. They are prepared by reacting a novolak with an alkylene oxide. These types of polyols have the advantage of having a high aromatic content, which is known to be industrially helpful for improving the pyrophoric reaction and may have a high functionality. However, formulators still need to use other polyols as well as amine-based catalysts and flame retardants to achieve the desired thermal, combustion and mechanical properties.

The Spray Polyurethane Foam (SPF) market is, for example, one of the fastest growing polyurethane areas due to SPF's ability to provide high insulation, excellent ability to reduce noise, and ability to retrofit existing buildings and infrastructure. However, many SPF formulations use small molecule organic and inorganic catalysts to provide fast reaction and phosphate or phosphate-chlorinated additives to develop and meet fire regulations ratings for buildings. Small molecule catalysts such as amines can volatilize during spray polyurethane installation, which presents a health hazard. Small molecule flame retardants that are consistently added to these formulations are under regulatory scrutiny due to concerns related to their impact on the environment.

Accordingly, there is an increasing demand for better performing rigid polyurethane foams with specific flammability specifications and acceptable physical properties. There is a need in the industry for polyols that have high reactivity towards isocyanates, inherent flame retardancy, high functionality for achieving desired properties, and allow the reduction or elimination of volatile amine-based catalysts and small molecule flame retardants.

Disclosure of Invention

In one broad embodiment of the present invention, an alkoxylated triazine-arylhydroxy-aldehyde condensate compound is disclosed. The compound is prepared by a process comprising, consisting of, or consisting essentially of: condensing the triazine-arylhydroxy-aldehyde condensate, optionally in the presence of a catalyst; and at least one alkoxylating agent to form an alkoxylated triazine-arylhydroxy-aldehyde condensate compound. The alkoxylating agent may be an alkylene oxide, either alone or in combination with an alkylene carbonate. In further embodiments, the alkoxylating agent may be an alkylene carbonate.

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

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

In another embodiment of the present invention, a process is provided which comprises reacting a triazine-aryl hydroxy-aldehyde condensate and at least one alkylene oxide, alone or in combination with an alkylene carbonate, optionally in the presence of a catalyst and forming an alkoxylated triazine-aryl hydroxy-aldehyde condensate composition. In one embodiment, the condensate composition is free of catalyst, free of flame retardant, free of mannich polyol, or a combination thereof. In one embodiment, the condensate composition is free of amine catalysts.

In another embodiment of the present invention, a polymer is provided which comprises using a formulation comprising a polyisocyanate and an isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate. An article can be prepared from the polymer. In one embodiment, the formulation is free of catalyst, free of flame retardant, free of mannich polyol, or a combination thereof. In one embodiment, the formulation is free of amine catalysts.

In another embodiment of the present invention, a process is provided that includes 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 to form a polymer. In one embodiment, the reaction mixture is free of catalyst, free of flame retardant, free of mannich polyol, or a combination thereof. In one embodiment, the formulation is free of amine catalysts. The method may further comprise applying the polymer to a substrate.

Detailed description of the invention

Embodiments of the present invention relate to alkoxylated triazine-arylhydroxy-aldehyde condensates, methods of making the alkoxylated triazine-arylhydroxy-aldehyde condensates, and the use of the alkoxylated triazine-arylhydroxy-aldehyde condensates to make polyurethane and polyisocyanurate resins.

The alkoxylated triazine-arylhydroxy-aldehyde condensate is formed by reacting the 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 a 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 a 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 the triazine monomer include compounds derived from aminotriazine groups such as 4-methyl-1, 3, 5-triazin-2-amine, 2-amino-4, 6-dimethyl-1, 3, 5-triazine, melamine, hexamethoxymethylmelamine, hexamethylolmelamine, guanamine, acetoguanamine, propionylguanamine, butyrylguanamine, benzoguanamine, vinylguanamine, 6- (hydroxyphenyl) -2, 4-diamino-1, 3, 5-triazine, and combinations thereof.

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

The aldehyde monomer includes compounds having one or more aldehyde functional groups (-CHO) and any aldehyde-producing compound. 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 include, but are not limited to, compounds such as formaldehyde, paraformaldehyde, acetaldehyde, isobutyraldehyde, benzaldehyde, acrolein, crotonaldehyde, salicylaldehyde, 4-hydroxybenzaldehyde, furfural, pyrrole-2-formaldehyde, cinnamaldehyde, trioxymethylene, paraldehyde, terephthalaldehyde, glyoxal, glutaraldehyde, and combinations thereof.

The triazine-arylhydroxy-aldehyde condensate can comprise a variety of triazine, arylhydroxy, and aldehyde combinations. In various embodiments, the condensate is melamine, phenol, and formaldehyde novolacs. Further details regarding the triazine-arylhydroxy-aldehyde condensates and their preparation can be found in U.S. patent nos. 6239248 and 9249251, both of which are incorporated herein by reference.

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

Suitable alkylene oxides may include linear aliphatic alkylene oxides, branched aliphatic alkylene oxides, cycloaliphatic alkylene oxides, aromatic alkylene oxides, alkyl aromatic alkylene oxides, alkylene oxides with ethers (commonly referred to as glycidyl ethers), and alkylene oxides with esters (commonly referred to as glycidyl esters).

Examples of suitable alkylene oxides may be one or more alkylene oxides selected from the group consisting of: ethylene oxide, propylene oxide, glycidyl, 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 can comprise from about 5 wt% to about 90 wt% of the triazine-arylhydroxy-aldehyde condensate and the at least one alkylene oxide reaction mixture. Alternatively, in one embodiment, the triazine-arylhydroxy-aldehyde condensate and the alkoxylating agent may be present in a ratio of reaction sites to alkoxylating agent, such as alkylene oxide and/or alkylene carbonate, of about 20:1 to about 1: 20.

Suitable alkylene carbonates, if present, may include linear aliphatic alkylene carbonates, branched aliphatic alkylene carbonates, aromatic alkylene carbonates, alkyl hydroxide carbonates, ethylene carbonates, acrylic carbonates, and ester carbonates. Examples of preferred alkylene carbonates may include one or more alkylene carbonates selected from: ethylene carbonate, propylene carbonate, butylene carbonate, glycerol carbonate, styrene carbonate, 1-chloro-propylene carbonate, isobutylene carbonate, cyclohexene carbonate, allyl carbonate, methacrylate carbonate, ethylene carbonate, allyl phthalate carbonate, 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 can be prepared from suitable monoepoxide compounds such as 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.

The alkylene carbonate may constitute from about 5 wt% to about 50 wt% of the triazine-arylhydroxy-aldehyde condensate and the at least one alkylene carbonate and optionally the at least one alkylene oxide reaction mixture. Alternatively, the triazine-arylhydroxy-aldehyde condensate and the at least one alkylene carbonate may be present in a ratio of reaction site to alkylene carbonate of from about 1:1 to about 1:2 is present. 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.

If both alkylene oxide and alkylene carbonate are present, these components may constitute from about 2 wt% to about 90 wt% of the triazine-aryl hydroxy-aldehyde condensate, the at least one alkylene oxide and the at least one alkylene carbonate reaction mixture. Alternatively, the combined components of the triazine-arylhydroxy-aldehyde condensate and the at least one alkylene oxide and the at least one alkylene carbonate may be present at the reaction site in a ratio of about 20:1 to about 1:20 of alkylene oxide and the at least one alkylene carbonate.

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

The reactive site is defined as any site having an unstable proton with a pKa of less than 40, for example a phenolic hydroxyl group, a primary hydroxyl group, a secondary hydroxyl group, a tertiary hydroxyl group, an amine hydroxyl group such as a primary amine, a secondary amine, an aromatic primary amine, or an aromatic secondary amine. A primary amine will have two reactive sites and a secondary amine will have one reactive site.

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

These components may be added together in any suitable manner. For example, the reaction may 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-aryl hydroxy-aldehyde condensate and then reacted until the alkylene oxide is consumed. In various embodiments, the alkylene oxide can be charged in bulk (bulk) under pressure to the molten triazine-arylhydroxy-aldehyde condensate and reacted to a specific pressure drop or until all alkylene oxide has been consumed.

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

Optionally, the reaction between the triazine-arylhydroxy-aldehyde condensate and the alkylene oxide may be carried out 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 may be used include, but are not limited to, 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 combinations thereof. Examples of the organic acid include oxalic acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, salicylic acid, benzoic acid, adipic acid, or p-toluenesulfonic acid; and examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and combinations thereof. The organic and inorganic acids may also be used to neutralize the reaction mixture.

In one embodiment, the formulation used to form the condensate is free of catalyst, free of flame retardant, free of mannich polyol, or a combination thereof. In one embodiment, the condensate does not contain an amine catalyst.

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

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensate compounds may be represented by formula I below.

R₆The functional group is represented by formula II or formula III. R of the formula I₇The functional group may be a hydrogen atom or represented by formula II or formula IV.

R₈And R₉May each independently be 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)₂NH (formula V), -N (formula IV) (formula V), -N (formula V)₂or-NH₂。

The structures of formulae II, III, IV and V are depicted below.

In the above formula, R₁And R₂Independently 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 and containing a hydroxyl group.

R₁₀May be a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and containing a hydroxyl group, a phenyl group, a vinyl group, a propenyl group, a phenyl group containing a hydroxyl group, a pyrrolyl group, or a furyl group.

R₁₁And R₁₂Each independently is 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 hydroxyphenyl group, or an alkyl group having 1 to 10 carbon atoms and at least one carbon substituted with i) a hydroxyl group, ii) a hydroxyphenyl group, or iii) a phenyl group. In various embodiments, R₁₁And R₁₂May combine to form a common aromatic ring with or without hydroxyl groups.

R₁₃And R₁₄Each independently of the others is 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)₂or-NH₂。

R₁₅、R₁₆And R₁₇Each independently of the others is 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 V), -N (formula IV) (formula V), -N (formula V)₂or-NH₂。

In the above formula, when an alkylene carbonate is used as the only 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 3 to 10. The monomers shown by m and n may be arranged in any order, combination or sub-combination.

In the above formula, when 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 shown by m and n may be arranged in any order, combination or sub-combination. In another embodiment, when 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 fed to the reaction mixture to produce 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 20. The monomers indicated by m and n may be arranged in any order, combination or sub-combination.

In the above formula, when both an alkylene oxide and an alkylene carbonate are used as the 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 shown by m and n may be arranged in any order, combination or sub-combination. In another embodiment, when both an alkylene oxide and an 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 an alkylene carbonate and an alkylene oxide are used as the alkoxylating agent, each x is independently 3 to 20, and each x' is independently 3 to 20. In another embodiment, when the alkoxylating agent is a combination of an alkylene oxide and an alkylene carbonate, when the average value of all x and x 'is greater than 2, the average value of all x and x' is greater than 2.

In various other embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensate typically has a nitrogen content of from about 0.5 wt% (weight percent) to about 41 wt%, for example from about 1 wt% to about 23 wt%, for example from about 5 wt% to about 15 wt%.

In various other embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensate typically has an aromatic content of from about 0.5 wt% (weight percent) to about 69 wt%, for example from about 5 wt% to about 40 wt%, for example from about 12 wt% to about 30 wt%.

Examples of alkoxylated triazine-arylhydroxy-aldehyde condensates are shown by the following formulas VIa-VIh:

the alkoxylated triazine-arylhydroxy-aldehyde condensates of the present invention typically have a viscosity at 25 ℃ of about 0.01 to 60 pascal seconds, for example a viscosity at 25 ℃ of about 0.01 to 30 pascal seconds. Any and all ranges within the range of 0.01 to 60 pascal seconds are included herein and disclosed herein, for example the alkoxylated triazine-arylhydroxy-aldehyde condensate has a viscosity in the solvent of 0.1 to 30 pascal seconds or 10 to 20 pascal seconds at 25 ℃. The alkoxylated triazine-arylhydroxy-aldehyde condensates of the present invention may additionally exhibit non-newtonian behavior such as shear thinning behavior, which may be influenced by the type of alkoxylating agent and the number of x and x's introduced via the alkoxylating agent.

The manufacture of the triazine-arylhydroxy-aldehyde condensate and the formation of the alkoxylated triazine-arylhydroxy-aldehyde condensate composition may be carried out in the same reactor or in different reactors. The manufacture of the triazine-arylhydroxy-aldehyde condensate and/or the formation of the alkoxylated triazine-arylhydroxy-aldehyde condensate composition may be carried out in a continuous, semi-continuous to batch, or batch type process and/or reactor.

The alkoxylated triazine-arylhydroxy-aldehyde condensates of this invention can be used as polyisocyanate-reactive compounds to make polyurethane and polyisocyanurate based polymers.

In one embodiment, the polymer may be prepared using 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. The polyisocyanate component may also be referred to as the "A side" during the polyurethane reaction. Alkoxylated triazine-arylhydroxy-aldehyde condensates, as described herein, of an isocyanate-reactive compound component, either alone or in combination with another polyol, may also be referred to as the "B-side" during the polyurethane reaction. In one embodiment, the formulation or reaction mixture is free of catalyst, free of flame retardant, free of mannich polyol, or a combination thereof. In one embodiment, the formulation is free of amine catalysts.

The at least one polyisocyanate comprises from about 33% to about 83%, such as from about 49% to about 51%, by weight of the reaction mixture, and the isocyanate-reactive compound comprises from about 13% to about 51%, such as from about 38% to about 40%, by weight of the reaction mixture, wherein the total amount of components equals 100% by weight of the reaction mixture. The reaction mixture may further include optional additive materials described herein, and if present, may be present in an amount of about 4 wt% to about 16 wt%, for example about 11 wt% to about 13 wt%, of the formulation or reaction mixture, with the total amount of components equaling 100 wt% of the reaction mixture.

In various embodiments, the reaction mixture is formed from 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 include, but are not limited to, m-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, cyclohexane-1, 4-diisocyanate, hexahydrotoluene diisocyanate, naphthylene-1, 5-diisocyanate, methoxyphenyl-2, 4-diisocyanate, diphenylmethane-4, 4 ' -diisocyanate, diphenylmethane-2, 4-diisocyanate, 4 ' -biphenylene diisocyanate, 3 ' -dimethoxy-4, 4 ' -biphenylene diisocyanate, 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate, 3 ' -dimethyldiphenylmethane-4, 4 ' -diisocyanate, 4 ', 4 "-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, polymeric diphenylmethane diisocyanate (PMDI), isophorone diisocyanate, toluene-2, 4, 6-triisocyanate, 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-diisocyanate and mixtures thereof are collectively referred to as MDI and all can be used. Polymeric forms of the compounds, such as polymeric diphenylmethane diisocyanate (PMDI), may also be used. Toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, and mixtures thereof are collectively referred to as TDI and all can be used.

Any of the foregoing polyisocyanates may be modified to include urethane, urea, biuret, carbodiimide, allophanate (allophonate), uretonimine, isocyanurate, amide or similar linkages. Examples of these types of modified isocyanates include various urethane 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, where a standard polyisocyanate is pre-reacted with a blocking agent containing active hydrogen groups, which may then be unblocked at a temperature greater than 40 ℃ (typically 100 ℃ to 190 ℃). Examples of blocking agents include, but are not limited to, gamma-caprolactam, phenol, methyl ketoxime, 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 may be used in combination with the alkoxylated triazine-arylhydroxy-aldehyde condensate include polyether polyols. They can be prepared by polymerizing an alkylene oxide onto an initiator compound having a plurality of active hydrogen atoms. Suitable initiator compounds include, but are not limited to, alkylene glycols, glycol ethers, glycerol, trimethylolpropane, sucrose, glucose, fructose, phenol formaldehyde condensates, ethylene diamine, hexamethylene diamine, diethanolamine, monoethanolamine, piperazine, aminoethylpiperazine, diisopropanolamine, monoisopropanolamine, methanolamine, dimethanolamine, and toluene diamine. An example of such a polyol is Poly-G74-376, a sucrose-initiated polyether polyol commercially available from Monument Chemical that is manufactured using ethylene oxide and propylene oxide.

Polyester polyols may also be used as part of the isocyanate-reactive compound. Polyester polyols include the reaction products of polyols, typically diols, with polycarboxylic acids or their anhydrides, typically dicarboxylic acids or dicarboxylic acid anhydrides. The polycarboxylic acids or anhydrides may be aliphatic, cycloaliphatic, 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 a mannich polyol. The most established mannich polyols in formulations, especially in spray foaming applications, are the reaction product of nonylphenol, formaldehyde and diethanolamine. Manufacturers of mannich polyols provide formulation flexibility by varying the ratio of formaldehyde, ethanolamine and alkoxylate to provide specific functionality and equivalent weight. The mannich polyol used as one of the polyols mentioned in the examples herein is a mannich polyol which is also nonylphenol initiated. In another embodiment, the isocyanate-reactive compound may be free of a mannich polyol. 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 at about 1% by weight to about 50% by weight. Any and all ranges between 1 and 50 weight percent are included herein and disclosed herein; for example, the alkoxylated triazine-arylhydroxy-aldehyde condensate may be present in the isocyanate-reactive compound at 5 wt% to 35 wt%, 15 wt% to 25 wt%, or 9 wt% to 21 wt%.

In various embodiments, it has been observed that the alkoxylated triazine-arylhydroxy-aldehyde condensate has a sufficiently high reactivity to render the catalyst optional. The reaction and/or reaction mixture of the alkoxylated triazine-arylhydroxy-aldehyde condensate and the polyisocyanate compound may be free of catalyst, e.g., free of amine catalyst. Further, the reaction and/or reaction mixture of the alkoxylated triazine-arylhydroxy-aldehyde condensate and the polyisocyanate compound may be catalyst-free, flame retardant-free, mannich polyol-free, or combinations thereof.

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

In various embodiments, it has been observed that the alkoxylated triazine-arylhydroxy-aldehyde condensate is sufficiently reactive such that no catalyst needs to be added for the polymer-forming reaction. The polyisocyanate and alkoxylated triazine-arylhydroxy-aldehyde condensate mixture may be free of catalyst, free of flame retardant, free of mannich polyol, or combinations thereof. In one embodiment, the condensate mixture may be free of amine catalysts.

Optionally, in various embodiments, the polyisocyanate and alkoxylated triazine-arylhydroxy-aldehyde condensate mixture may also include a catalyst. Examples of catalysts include, but are not limited to, tertiary amines such as dimethylbenzylamine, 1, 8-diaza (5,4,0) undecane-7, pentamethyldiethylenetriamine, dimethylcyclohexylamine, and triethylenediamine. Potassium salts such as potassium acetate and potassium octoate may also be used as catalysts. In various embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensate minimizes the use of catalyst or allows the formulation to be catalyst free as described herein by its inherent high reactivity to isocyanates (autocatalysis).

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehyde condensate further comprises a diluent. Suitable diluents include, but are not limited to, polyglycols, etherified polyglycols, dibasic esters of acids, and combinations thereof. Examples of diluents include, but are not limited to, 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.

Depending on the particular type of polymer produced and the requisite properties of the polymer, a wide variety of additional materials may be present during the reaction of the polyisocyanate compound and the alkoxylated triazine-arylhydroxy-aldehyde condensate. These additive materials include, but are not limited to, surfactants, foaming agents, cell openers, fillers, pigments and/or colorants, desiccants, reinforcing agents, biocides, preservatives, antioxidants, flame retardants, and combinations thereof. The additive material may be present in an amount of about 0 wt% to about 20 wt%, such as about 4 wt% to about 16 wt%, such as about 11 wt% to about 13 wt% of the formulation or reaction mixture.

If included, the flame retardant may be a phosphorus-containing flame retardant. Examples of phosphorus-containing flame retardants include, but are not limited to, triethyl phosphate (TEP), triphenyl phosphate (TPP), trichloropropyl phosphate (TCPP), dimethylpropane phosphate, resorcinol bis (diphenyl phosphate) (RDP), Bisphenol A Diphenyl Phosphate (BADP), and tricresyl phosphate (TCP), dimethyl methylphosphonate (DMMP), cresyldiphenyl phosphate, and aluminum diethylphosphinate.

The relative amounts of polyisocyanate and alkoxylated triazine-arylhydroxy-aldehyde condensate are selected to produce the polymer. The ratio of these components is often referred to as "isocyanate index" which means 100 times the ratio of isocyanate groups to isocyanate-reactive groups provided by the alkoxylated triazine-arylhydroxy-aldehyde condensate. The isocyanate index is typically at least 50 and may be up to 1000 or more, for example from about 50 to about 900. Rigid polymers such as structured polyurethanes and rigid foams are typically manufactured using an isocyanate index of 90-200. When preparing soft or semi-soft polymers, the isocyanate index is generally from 70 to 125. Polymers containing isocyanurate groups are often made at isocyanate indices 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 achieved by: the reaction mixture is subjected to conditions sufficient to cause the polyisocyanate compound and the alkoxylated triazine-arylhydroxy-aldehyde condensate to react to form a polymer.

An example would be to mix the alkoxylated triazine-arylhydroxy-aldehyde condensate with pMDI at ambient conditions for 10 seconds to produce a reaction between the hydroxyl groups and the isocyanate. The reaction generates heat and, depending on the length of alkoxylation, can produce either a rigid or flexible foam.

A wide variety of polymers can be made in accordance with the present invention by proper selection of the particular alkoxylated-triazine-arylhydroxy-aldehyde condensate, the particular polyisocyanate, the presence of the optional materials and reaction conditions described below. The process of the present invention can be used to produce various types of polyurethane and/or polyisocyanurate polymers including rigid polyurethane foams, sealants and adhesives (including moisture curable types), hot melt powders, wood adhesives, cast elastomers, soft or semi-soft reaction injection moldings, rigid structural composites, flexible polyurethane foams, adhesives, cushioned and/or integral backings for carpets and other textiles, semi-flexible foams, pipe insulation, automotive cavity seals, automotive noise and/or vibration damping, 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 can be used in substrates as part of a polymer production process, such as point-of-use applications, or applied after polymer production is complete for subsequent use in an application process. Suitable substrates may include inorganic materials such as silica or metals, or organic materials such as wood or plastics, or combinations thereof. Examples of suitable substrates include supports and supportive substrates, wood, building materials, and structural surfaces, among others.

Example (b):

for the examples, the triazine-arylhydroxy-aldehyde condensate compositions were prepared using the method described in U.S. patent No. 9249251, which is incorporated herein by reference to the extent not inconsistent with the present invention.

The following procedure was used for examples 1-6 for the data reported in tables 1 and 2.

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

Hydroxyl number: this value was obtained using the titration method specified by the American Petroleum chemist's Association (AOCS) CD 13-60 method.

Solubility in water of 5%: it was determined by: 5g of the materials of examples 1-6 were mixed with 95g of distilled deionized water for 30 minutes and the visual appearance of the system was examined. If the system is clear and does not exhibit sediment, it is considered soluble, and if the system exhibits any haze, turbidity or sediment, it is considered insoluble.

Viscosity at 30 deg.C: the viscosity of the material at 30 ℃ is determined from a parallel plate rheometer operating in rotating mode with a scanning shear rate of 0.1-100 l/s. The material viscosity was extrapolated to 0 shear viscosity and reported in mpa.s.

pH (5% in IPA/water): the pH was determined by: the material was dissolved in 50% isopropyl alcohol (IPA) in water and the pH of the entire system was read using a calibrated pH probe.

Control substance

Triazine-arylhydroxy-aldehyde condensate control samples were prepared according to the method of U.S. patent No. 9249251. It is briefly described in part as follows. 546.0g of phenol (5.8mol), 1.1g of benzoic acid and 79.1g of melamine (0.63mol) were charged to a reaction vessel to form a reaction mixture. The reaction mixture was heated to 80 ℃ and 55.8g of formaldehyde in the form of a 50% solution in water were added over 40 minutes. The reaction was distilled to 123 ℃ at atmospheric pressure after the addition and maintained at 123 ℃ for 2 hours. The reaction mixture was then cooled to 80 ℃ and 37.2g of formaldehyde in the form of a 50% solution in water was added over 30 minutes, then distilled to 123 ℃ under atmospheric pressure and maintained at 123 ℃ for 2 hours. The reaction mixture was then further distilled at atmospheric pressure to 165 ℃ and then gradually vacuum distilled over 3 hours to 27 inches of mercury while maintaining 165 ℃ and then heated to 175 ℃ while maintaining 27 inches of mercury. The reaction mixture was kept at 175 ℃ for 1 hour and then steam-sparged for 60 minutes while under vacuum distillation. A total of 426.6g of distillate were removed and 212.9g of arylhydroxy-aldehyde condensate were discharged from the reaction vessel and exhibited brittle and solid-like material properties upon cooling.

Example 1

500g of the triazine-arylhydroxy-aldehyde condensate formed from the comparative example and 50% of potassium hydroxide in methanol were charged to a 2L pressure reactor equipped with a mechanical stirrer, reflux condenser, thermocouple and thermocouple-controlled heating mantle. The reactor was flushed with nitrogen to remove air and heated to 90 ℃ followed by vacuum dehydration at 120 ℃ to remove traces of water and methanol. The mixture is then heated to a temperature of 150 ℃ and 160 ℃. Then, 20% of 1015g of ethylene oxide was charged into the flask to initiate the reaction, followed by adding the remaining ethylene oxide to 4.0kg/cm²The pressure of (a). The reaction mixture was allowed to stand at 165 ℃ at 4.0kg/cm²Then cooled to 70-75 ℃ and neutralized to pH 7-8. The yield was 87%.

Example 2

500g of the triazine-arylhydroxy-aldehyde condensate formed from the comparative example and 50% of potassium hydroxide in methanol were charged to a 3L pressure reactor equipped with a mechanical stirrer, reflux condenser, thermocouple and thermocouple-controlled heating mantle. The reactor was flushed with nitrogen to remove air and heated to 90 ℃ followed by vacuum dehydration at 120 ℃ to remove traces of water and methanol. The mixture is then heated to a temperature of 150 ℃ and 160 ℃. Then, 20% 3254g of ethylene oxide was then charged to the flask to initiate the reactionThe remainder of the ethylene oxide should then be added to 4.0kg/cm²The pressure of (a). The reaction mixture was allowed to stand at 165 ℃ at 4.0kg/cm²Then cooled to 70-75 ℃ and neutralized to pH 7-8. The yield was 85%.

Example 3

135g of the triazine-arylhydroxy-aldehyde condensate formed from the comparative example and 50% of potassium hydroxide in methanol were charged to a 2L pressure reactor equipped with a mechanical stirrer, reflux condenser, thermocouple and thermocouple-controlled heating mantle. The reactor was flushed with nitrogen to remove air and heated to 90 ℃ followed by vacuum dehydration at 120 ℃ to remove traces of water and methanol. The mixture is then heated to a temperature of 150 ℃ and 160 ℃. Then, 20% of 1370g of ethylene oxide was then charged into the flask to initiate the reaction, followed by adding the remaining ethylene oxide to 4.0kg/cm²The pressure of (a). The reaction mixture was allowed to stand at 165 ℃ at 4.0kg/cm²Then cooled to 70-75 ℃ and neutralized to pH 7-8. The yield was 92%.

The physical properties of the compositions of examples 1-3 were tested. The results are shown in table 1: triazine-arylhydroxy-aldehyde condensates alkoxylated with ethylene oxide are among the physical properties.

TABLE 1

Parameter(s)	Control substance	Example 1	Example 2	Example 3
					Water%	0.1	0.5	0.1	0.2
Hydroxyl number (mg KOH/g)	739	368	209	158
					Solubility in water of 5%	Is insoluble	Is insoluble	Is insoluble	Soluble and clear
Viscosity (mPa.s) at 30 ℃	Solid body	13000	370	900
					pH (5% in IPA/water)	6.5	7.2	7.4	7.6

Table 1 demonstrates the performance of the alkoxylated triazine-arylhydroxy-aldehyde condensates after alkoxylation and shows the control before alkoxylation. The properties, in particular viscosity, hydroxyl number, water% and pH, are important for the application of the alkoxylated triazine-arylhydroxyl-aldehyde condensate in the preparation of polyurethane foams. The solubility in water indicates whether the alkoxylated triazine-arylhydroxy-aldehyde condensate formed is hydrophilic or hydrophobic. The example 3 condensate is soluble in water and thus hydrophilic or water miscible, and the examples 1 and 2 condensates are insoluble and thus hydrophobic. These examples further indicate that increasing the length of alkoxylation with ethylene oxide corresponds to a more hydrophilic condensate, thereby increasing the water solubility until a water soluble product is formed.

In addition, alkoxylation produces materials that are liquid at 30 ℃, and enables them to be used in liquid polyurethane applications such as mixing with other polyols with the addition of heat or where specialized processing conditions are required. Finally, the hydroxyl number of the control sample at 739mg KOH/g is extremely high and would require a large amount of isocyanate to maintain the typical isocyanate index for polyurethane foam, while a hydroxyl number of 150-400mg KOH/g is more suitable for most polyurethane foam applications.

Example 4

408g of the triazine-arylhydroxy-aldehyde condensate formed from the comparative example and 50% of potassium hydroxide in methanol were charged to a 2L pressure reactor equipped with a mechanical stirrer, reflux condenser, thermocouple and thermocouple-controlled heating mantle. The reactor was flushed with nitrogen to remove air and heated to 90 ℃ followed by vacuum dehydration at 120 ℃ to remove traces of water and methanol. The mixture is then heated to a temperature of 150 ℃ and 160 ℃. Then, 20% of 1092g of propylene oxide was then charged into the flask to initiate the reaction, followed by adding the remaining propylene oxide to 4.0kg/cm²The pressure of (a). The reaction mixture was allowed to stand at 165 ℃ at 4.0kg/cm²Then cooled to 70-75 ℃ and neutralized to pH 7-8. The isolated yield was 48%.

Example 5

185g of the triazine-arylhydroxy-aldehyde condensate formed from the comparative example and 50% of potassium hydroxide in methanol were charged to a reactor equipped with a mechanical stirrer, reflux condenser, thermocouple andthermocouple-controlled heating mantle 2L pressure reactor. The reactor was flushed with nitrogen to remove air and heated to 90 ℃ followed by vacuum dehydration at 120 ℃ to remove traces of water and methanol. The mixture is then heated to a temperature of 150 ℃ and 160 ℃. Then, 20% 1316g of propylene oxide was then charged to the flask to initiate the reaction, followed by the addition of the remainder of the propylene oxide to 4.0kg/cm²The pressure of (a). The reaction mixture was allowed to stand at 165 ℃ at 4.0kg/cm²Then cooled to 70-75 ℃ and neutralized to pH 7-8. The isolated yield was 86%.

Example 6

105g of the triazine-arylhydroxy-aldehyde condensate formed from the comparative example and 50% of potassium hydroxide in methanol were charged to a 2L pressure reactor equipped with a mechanical stirrer, reflux condenser, thermocouple and thermocouple-controlled heating mantle. The reactor was flushed with nitrogen to remove air and heated to 90 ℃ followed by vacuum dehydration at 120 ℃ to remove traces of water and methanol. The mixture is then heated to a temperature of 150 ℃ and 160 ℃. Then, 20% 1405g of propylene oxide was then charged into the flask to initiate the reaction, followed by adding the remaining propylene oxide to 4.0kg/cm²The pressure of (a). The reaction mixture was allowed to stand at 165 ℃ at 4.0kg/cm²Then cooled to 70-75 ℃ and neutralized to pH 7-8. The yield was 89%.

The physical properties of the compositions of examples 4-6 were tested. The results are shown in table 2: triazine-arylhydroxy-aldehyde condensates alkoxylated with propylene oxide are among the physical properties.

TABLE 2

Parameter(s)	Control substance	Example 4	Example 5	Example 6
					Water%	0.1	0.2	0.3	0.4
Hydroxyl number (mg KOH/g)	739	240.2	210	180
					Solubility in water of 5%	Is insoluble	Is insoluble	Is insoluble	Is insoluble
Viscosity (cps) at 30 deg.C	Solid body	522	890	500
					pH (5% in IPA/water)	6.5	7.5	7.7	7.5

Table 2 shows the properties of the alkoxylated triazine-arylhydroxy-aldehyde condensate after alkoxylation with propylene oxide and compares the results with a triazine-arylhydroxy-aldehyde condensate control. This property, in particular viscosity, hydroxyl number, water% and pH, is important for the application of the alkoxylated triazine-arylhydroxy-aldehyde condensate to the preparation of polyurethane foams. Solubility in water is used as an indication of whether the alkoxylated triazine-arylhydroxy-aldehyde condensate formed is hydrophilic or hydrophobic, and it can be seen that the alkoxylated triazine-arylhydroxy-aldehyde condensates prepared with propylene oxide are all hydrophobic and insoluble in water, even though long propoxylation lengths are used as can be seen in example 6.

Example 7: viscosity of alkoxylated triazine-arylhydroxy-aldehyde condensates

An ARES-G2 rheometer (TA instruments) equipped with stainless steel parallel plates was operated in a rotary mode to determine the viscosity of examples 1-6 at 25 deg.C, 30 deg.C, 35 deg.C and 40 deg.C. The viscosity is determined from a "zero shear" approximation, wherein the viscosity is determined as a function of shear rate (0.1-100 l/s). The zero shear viscosity is determined by extrapolating the viscosity curve to zero shear, which takes 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 reported in the newtonian region of the viscosity curve. 10 data points were measured for each magnitude change in shear rate, such as 10 points between 0.1l/s and 1 l/s. Lower temperatures are determined when the material exhibits non-Newtonian behavior such as shear thinning. The results are shown in tables 3a-3b below: viscosity results for the condensates of examples 1-6. Examples exhibiting shear thinning are indicated by (ST).

TABLE 3a

TABLE 3b

Tables 3a and 3b show the temperature dependence of the viscosity of different alkoxylated triazine-arylhydroxy-aldehyde condensates. Temperature has a significant effect on product viscosity and in some cases a temperature change of 5 ℃ reduces the viscosity of newtonian alkoxylated triazine-arylhydroxy-aldehyde condensates by 40% and by 93% of non-newtonian alkoxylated triazine-arylhydroxy-aldehyde condensates. This data is important to polyurethane formulators because the viscosity of each component in a polyurethane system can have a significant impact on the overall performance of the final system.

Based on the results of tables 1-4, the alkoxylated triazine-arylhydroxy-aldehyde condensates can be used as rheology modifiers for polyurethane crosslinkers to further adjust the viscosity of polyurethane systems.

Example 8 (polyurethane)

8.85g of an alkoxylated triazine-arylhydroxy-aldehyde condensate having an average repeat unit of 3 ethylene oxide units was mixed with 10g of pMDI with a metal spatula for 20 seconds. The mixture exhibited an exotherm within 20 seconds. The material appeared slightly foamed due to residual water, hardened and was not tacky after 30 seconds. The final material is a solid, intractable material that is rigid and has a foam-like structure.

Example 9

5.0g of an alkoxylated triazine-arylhydroxy-aldehyde condensate with an average repeat unit of 8 ethylene oxide units was mixed with 10g of pMDI with a metal spatula for 10 seconds. The mixture exhibited an exotherm within 10 seconds. The material appeared slightly foamed, hardened due to residual water and was not tacky after 30 seconds. The final material is an intractable material with some flexibility and a foam-like structure.

Example 10

3.8g of an alkoxylated triazine-arylhydroxy-aldehyde condensate with an average repeat unit of 15 ethylene oxide units was mixed with 10g of pMDI with a metal spatula for 10 seconds. The mixture exhibited an exotherm within 15 seconds. The material appeared slightly foamed due to residual water and was not tacky after 30 seconds. The material is a flexible foam even when at room temperature.

Example 11

A 5mg sample was cut from the material produced in example 9 and placed in a hermetically sealed differential scanning calorimeter pan. The sample is exposed to a heating/cooling/heating cycle from-50 ℃ to 180 ℃ at a ramp rate of 10 ℃/min and is uncontrollably quenched to-50 ℃ in the cooling cycle. The first heating cycle confirmed that the material exhibited an unbiased (partial) cure with a peak exotherm temperature of 95 ℃ and a total enthalpy of 23.7J/g. The glass transition temperature from the first heating sweep was 14 ℃ and on the second heating sweep was 34 ℃.

Example 12

A 5mg sample was cut from the material produced in example 10 and placed in a hermetically sealed differential scanning calorimeter pan. The sample is exposed to a heating/cooling/heating cycle from-50 ℃ to 180 ℃ at a ramp rate of 10 ℃/min and is uncontrollably quenched to-50 ℃ in the cooling cycle. The first heating cycle confirmed that the material exhibited complete curing and did not exhibit an exothermic transition. The glass transition temperatures from the two heating scans were 9.8 ℃ and 10 ℃.

Example 13

A 5mg sample was cut from the material produced in example 11 and placed in a hermetically sealed differential scanning calorimeter pan. The sample is exposed to a heating/cooling/heating cycle from-80 ℃ to 180 ℃ at a ramp rate of 10 ℃/min and is uncontrollably quenched to-50 ℃ in the cooling cycle. The first heating cycle confirmed that the material exhibited complete curing and did not exhibit an exothermic transition. The glass transition temperatures from the two heating scans were-38 ℃ and-37 ℃.

Method of thermogravimetric analysis

A10 mg sample was cut from the material produced in example 9, 10 or 11, placed in an alumina thermogravimetric crucible, and removed from the chamberThe temperature was heated to 1000 ℃. The onset of degradation is through weight loss 5 (T)_d5％) And 10% (T)_d10％) And peak degradation temperature calculated from the derivative of the weight curve (%/deg.C). The results are reported in table 4: thermogravimetric analysis results.

TABLE 4

Length of ethoxylation	Peak degradation	Td5％	Td10％
				Example 11	397	223	255
Example 12	406	264	295
				Example 13	407	262	314

Table 4 indicates that the polyurethanes prepared from examples 11, 12 and 13 exhibit different thermal stabilities starting from the degradation. Degradation started by 5% (T)_d5％) And 10% (T)_d10％) Is determined by the weight loss of. Example 13 exhibits the highest thermal stability and T_d5％Is 262 ℃ and T_d10％Is 314 ℃. The polyurethane from example 13 exhibited about 6% greater thermal stability than example 12 and 18% greater thermal stability than example 11. This indicates that the ethoxylation length plays an important role in the thermal stability of the final polyurethane polymer.

Process for preparing foam

Foams were prepared using a high torque mixer (CRAFSTMAN 10-inch rotary bed, model 137.219000) at a speed of 3100 rpm. The polyol component and the isocyanate component of the foam system were mixed for 5 seconds. Thereafter, the mixture was transferred to an open cake box before cream time and allowed to rise. The foam was prepared by pouring the foaming mixture into a 9 "x 5" sized cake box. The foams were used to evaluate cream time, gel time, rise time, tack free time, density and visual appearance of the cell structure.

For examples 14-20, Lupranate M20S was polymeric methylene diphenyl diisocyanate (pMDI), available from BASF Corporation.

Example 14

Polyurethane foams were prepared according to the methods herein by reacting Lupranate M20S (a polymeric methylene diphenyl diisocyanate where the isocyanate index is 110) (a side) with a polyol component prepared from the corresponding components in table 5 (B side). The mixing time was kept constant and cream time, gel time, rise time and tack free time were all measured after the mixture had been poured into a polyethylene lined cardboard box. The foam formed had a density of 29.52 kg/m and had a uniform and coarse cell structure.

Example 15

Polyurethane foams were prepared according to the methods herein by reacting Lupranate M20S (a polymeric methylene diphenyl diisocyanate where the isocyanate index is 110) (a side) with a polyol component prepared from the corresponding components in table 5 (B side). The mixing time was kept constant and cream time, gel time, rise time and tack free time were all measured after the mixture had been poured into a polyethylene lined cardboard box. The density of the foam formed was 30.69 kg/m and had a uniform and fine cell structure.

Example 16

Polyurethane foams were prepared according to the methods herein by reacting Lupranate M20S (a polymeric methylene diphenyl diisocyanate where the isocyanate index is 110) (a side) with a polyol component prepared from the corresponding components in table 5 (B side). The mixing time was kept constant and cream time, gel time, rise time and tack free time were all measured after the mixture had been poured into a polyethylene lined cardboard box. The foam formed had a density of 28.45 kg/m and had a uniform and slightly coarse cell structure.

Example 17

Polyurethane foams were prepared according to the methods herein by reacting Lupranate M20S (a polymeric methylene diphenyl diisocyanate where the isocyanate index is 110) (a side) with a polyol component prepared from the corresponding components in table 5 (B side). The mixing time was kept constant and cream time, gel time, rise time and tack free time were all measured after the mixture had been poured into a polyethylene lined cardboard box. The foam formed had a density of 30.23 kg/m and had a uniform and fine cell structure.

Example 18

Polyurethane foams were prepared according to the methods herein by reacting Lupranate M20S (a polymeric methylene diphenyl diisocyanate where the isocyanate index is 110) (a side) with a polyol component prepared from the corresponding components in table 5 (B side). The mixing time was kept constant and cream time, gel time, rise time and tack free time were all measured after the mixture had been poured into a polyethylene lined cardboard box. The foam formed had a density of 37.25 kg/m and had a very fine cell structure.

Example 19

Polyurethane foams were prepared according to the methods herein by reacting Lupranate M20S (a polymeric methylene diphenyl diisocyanate where the isocyanate index is 110) (a side) with a polyol component prepared from the corresponding components in table 5 (B side). The mixing time was kept constant and cream time, gel time, rise time and tack free time were all measured after the mixture had been poured into a polyethylene lined cardboard box. The foam formed had a density of 28.90 kg/m and had a fine cell structure.

Example 20

Polyurethane foams were prepared according to the methods herein by reacting Lupranate M20S (a polymeric methylene diphenyl diisocyanate where the isocyanate index is 110) (a side) with a polyol component prepared from the corresponding components in table 5 (B side). The example 20 formulation contained no catalyst. The mixing time was kept constant and cream time, gel time, rise time and tack free time were all measured after the mixture had been poured into a polyethylene lined cardboard box. The density of the foam formed was 42.36 kg/m.

For table 5 below: the materials and amounts used in the B-side polyol formulations of examples 14-20 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-G74-376 is a sucrose-initiated polyether polyol made from ethylene oxide and propylene oxide, commercially available from monomer Chemical.

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

The diluent DBE ester is a mixture of dibasic esters of methyl and ethyl esters of adipic, succinic and glutaric acids, commercially 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) condensates of table 5 were prepared by the following procedure. 1000g of triazine-arylhydroxy-aldehyde condensate, 50g of glycerol, 6.6g of potassium hydroxide dissolved in 13.3g of methanol are charged to a 5L pressure reactor equipped with a mechanical stirrer, reflux condenser, thermocouple and thermocouple-controlled heating mantle. The reactor was then flushed with nitrogen to remove air and heated to 90 ℃ followed by vacuum dehydration at 120 ℃ to remove traces of water and methanol. The mixture is then heated to a temperature of 140 ℃ and 150 ℃. 59.25g of propylene oxide were then charged to the vessel and allowed to react, after which the reaction mixture was heated to a temperature of 155-160 ℃. 2200g of ethylene oxide are then added to 3.5-4.0kg/cm²The pressure of (a). After completion, the reaction mixture was then cooled to 70-75 ℃ and neutralized with 16g of salicylic acid. The yield was 95% and the material had a viscosity at 30 ℃ of 12400mPa.s, OH #, 364mg KOH/g, and a moisture content of 0.3%.

Table 5.

Table 5 shows the different formulation variations in the use of the alkoxylated triazine-arylhydroxy-aldehyde condensates prepared from example 1, and example 16 represents a control formulation without alkoxylated triazine-arylhydroxy-aldehyde condensates. The reactivity properties of the resulting polyurethane foams are shown in table 6. The method for measuring the reactivity in Table 6 was performed according to ASTM D7487-13e 1. Examples 15, 18 and 20 do not contain mannich (base) polyols. Example 20 contained no catalyst.

The reactivity properties of the resulting polyurethane foams are shown in table 6. Method for measuring reactivity in table 6: the reactivity of the polyurethane foam examples was accomplished according to ASTM D7487-13e 1.

TABLE 6

The reactivity of the foam formulation was evaluated based on the time it took to reach a milky, gelled, rising and non-tacky state. The smaller the time it takes to reach these states, the faster the reactivity of the formulation. From table 6, example 18, which contained the greatest concentration of alkoxylated triazine-arylhydroxy-aldehyde condensate, exhibited the highest reactivity of all the polyurethane foams produced, and was significantly faster than example 16, which served as a control. Examples 14 and 18 are direct comparisons of the reactivity between mannich polyols and alkoxylated triazine-arylhydroxy-aldehyde condensates.

It is clear that the alkoxylated triazine-arylhydroxy-aldehyde condensate is significantly more reactive than the mannich polyol. In addition, examples 16, 19, 15 and 18 illustrate the effect of increasing the concentration of the alkoxylated triazine-arylhydroxy-aldehyde condensate. When the concentration of the alkoxylated triazine-arylhydroxy-aldehyde condensate in these examples was increased from 0% to 10% to 15% to 30%, respectively, the reactivity also increased consistently as shown by the decrease in cream, gel, rise and tack free time.

Thus, the data in table 5 demonstrate the significantly higher reactivity of the alkoxylated triazine-arylhydroxy-aldehyde condensates compared to the reference polyols. The table also shows that the use of the novel polyols of the described invention can minimize or eliminate the use of mannich base polyols or small molecule amine catalysts in the formulation, which can cause a wide variety of human health problems, including glaucoma (Glaucopsia) and respiratory irritation.

Furthermore, due to the high functionality and aromaticity of the alkoxylated triazine-arylhydroxy-aldehyde condensate, the formulator may be able to develop a polyurethane composition without catalyst and without additional polyol, which may simplify complex formulations and minimize errors in producing B-side formulations. Examples of such formulations may be alkoxylated triazine arylhydroxy-aldehyde condensates, suitable surfactants, suitable blowing agents and suitable flame retardants.

The flame retardant performance data is provided in table 7 below: the combustion characteristics of examples 14-19.

TABLE 7

The burn rate and the weight retention after burning were measured using the modified ASTM D4986 flammability test in the cell. In this in-house test, bernzimatic torch TS4000 was used. The flammability test is relatively simple and is designed for relative comparison between different foam types. Lower mm/rate and higher mass retention indicate better response to fire or improved fire resistance.

Table 7 shows the effect of the polyol on the flame reaction of the foam. In examples 16, 19, 15 and 18, respectively, the burn rate consistently decreased as the concentration of the alkoxylated triazine-aryl hydroxy-aldehyde condensate increased from 0% to 10% to 15% to 30%, respectively, and the foam exhibited self-extinguishing properties at a maximum concentration of 30% in the absence of both the sugar-based polyether and the mannich polyol. Higher mass retention of residue is also a direct result of improved flame retardancy. Example 16, the mass retention of the control sample was 45%; the mass retention of example 18 with 30% of alkoxylated triazine-arylhydroxy-aldehyde condensate was 87%.

In addition to allowing simplification of the B-side formulation, it is further expected that the alkoxylated triazine aryl hydroxyl-aldehyde condensate will have better miscibility with aromatic isocyanates and blowing agents such as pentanes and their associated isomers, hydroxyfluorinated olefins, hydroxyfluorinated hydrocarbons and other halogenated blowing agents when compared to common polyols such as sucrose polyether polyols or other polyethers, mannich polyols, aromatic polyester polyols, ethylenediamine polyether polyols of sufficient hydrophilicity.

Finally, the alkoxylated triazine-arylhydroxy-aldehyde condensates have demonstrated a relatively high onset of thermal degradation when reacted with isocyanates and this can significantly improve the flame retardant properties of typical polyurethane foams or associated articles due to the nitrogen content present in the polyol being able to act synergistically with the phosphorus-containing compounds.

While the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein.