JPH01500908A - Compound and manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Compound and manufacturing method The present invention relates to compounds, processes and products.

In a particular aspect, the present invention relates to brominated phenolic esters and Mixing with prepolymers to improve certain physical properties of materials synthesized from polymers Concerning their use in objects. The additive of the present invention has flame retardant properties, surfactants and a compound selected from the group of brominated phenol esters that exhibits It is a mixture of them.

In a special embodiment of the invention, the additive is an isocyanate prepolymer or Flame-retardant polyurethane mixed with any polyurethane-based polyol prepolymer This provides a method for producing tan foam, in which molded modified prepolymer is Polyurethane foam is mixed sequentially with Lyol prepolymer or isocyanate, respectively. form.

The present invention is characterized in that the amount of combustion retardation is shown in the accompanying drawings and the compound of formula A compound of formula X11 (where Xl and X2 are oxygen or sulfur, and RO- is , 2.4.6-) which is a ribromophenoxy group) It provides retan foam.

Furthermore, the present invention has the following advantages as shown in the accompanying drawings regarding the amount of combustion retardation regarding the foam that can be generated. The compound of formula X1 and the compound of formula 111 shown in the attached drawings (however, Xt and X2 are is oxygen or sulfur, and RO- is 2,4.6-tribromophenoxy group ), it provides a polyurethane foam prepolymer containing a mixture of Ru.

Preferably Xl and X2 are both oxygen or sulfur.

The foam or prepolymer further comprises a compound of formula V as described in the accompanying drawings. But that's fine.

Prepolymers can be polyols or isocyanates. The latter is preferred .

The prepolymer preferably consists of an organic base. This base is preferably selected from thylamine, ethylenediamine and triethanolamine.

Preferably, the compound of formula X1 is present in the mixture in an amount of about 70-80% by weight. Ru.

Preferably, the compound of formula Xl1 is present in the mixture in an amount of about 20 to 30% by weight. do.

Preferably, said compound XIII is present in said mixture in an amount of about 3 to 8%. .

Preferably, the mixture contains 2y2-20 1% by weight, more preferably 8-10 1% by weight present in the prepolymer.

Preferably the organic base is present in the mixture in an amount of about 6-8% by weight.

The present invention relates to a compound of formula 11 shown in the accompanying drawings (where RO- is 2,4.6-to which is a ribromophenoxy group) or a mixture containing said compound. It is.

Various particularly preferred embodiments of the invention will now be described.

In a preferred embodiment, the present invention comprises compounds of formulas 1 to V as shown in the accompanying drawings. The use of five brominated phenol esters is provided.

Compound II, which is a preferred embodiment of the additive, does not appear to have been described hitherto. Burning We do not believe that the use of compound Iv as a baking retardant has been described to date. people Two earlier publications, Benbow and Gries (1975) Compassion A Frame Vol. 24, pp. 217-230 [Benbow & Cullis (1975), Combustion and Flame V, 24.　 p217-230)] is a compound for flame retardation of flexible polyurethane foam. describes the use of III. Its use is primarily used by its authors due to its poor solubility. is considered to be insufficient. Compound I for combustion retardation of flammable materials, Uses of III and V, although noted, are always consistent with those listed here and applicable. and mixing.

Widespread demand for urethane prepolymers rather than finished polymers is due to long-term storage This requires the production of prepolymers that have high stability over time. This is mainly due to For the selection of additives, including combustion retardants, for precipitation and/or neutralization of the catalyst It imposes strict restrictions. Compound II in either type of prepolymer The solubility of purified preparations of is limited. In other words, compound materials exhibit higher solubility. However, at high concentrations it still tends to settle at temperatures below 20°C. But long , an incompletely esterified preparation of Compound I containing some Compound II More soluble in polymers. Similarly, any compound containing some compound 1”/ Incompletely esterified preparations of Compound III are more soluble in each prepolymer. It is. Either these preparations alone or when mixed homogeneously with compound V, It readily produces true solutions that appear to be stable indefinitely.

The acidity introduced by either compound II or V is During isocyanate mixing, part of the amine catalyst in the system results in a reduced rate of foaming. Partially neutralize. This effect is at least reduced by the addition of organic amines. Some of these have been successfully tested.

Diesters (chemical compounds) relative to their corresponding triesters in isocyanates The remarkable effect of compounds II and IV) is shown in the reactions of the accompanying drawings in which R1 represents an organic functional group. 1 (as proposed, isocyanate monophosphate residues and isocyanate We believe that this is due to reversible mixing with nate residues.

The forward reaction proceeds at low temperatures, but the equilibrium shifts significantly toward the reverse reaction at temperatures above 40°C. Moving. Therefore, when mixing isocyanate and polyol prepolymers, At the temperature brought about by the exothermic reaction, incyanate forms a urethane bond. It is released for immediate recombination with the hydroxyl residue that forms. Its esterification In poor form, the diester (compound 11 or I''/) is fully solubilized. as well as the phosphoric acid ester (compound I or II I) and phosphite (compound V). assist in the development of

isocyanates with diesters and their related triesters. this is one major issue regarding flame retardants in polyurethane foam. thus overcoming the problem of non-uniform dispersion and therefore non-uniform protection against combustion.

The following example provides a method for making the additive. Esters originally from phenol The ester of promol (2,4,6-tribromophenol) generated at the position prepared in acetone solution by

Example In the first method, the phenolacetone solution is mixed with bromine in a 1:5.2 ratio. phenol/bromine (w/w) to produce promol and then heat the mixture at 15°C and 3 Mixed with phosphorus tribromide (1,05:1 phenol/bromine) at a temperature between 0°C W/W) to produce tripromole phosphite ester.

The initial phenol concentration in acetone was approximately 80% V/*, but this volume , often varied widely by producing non-critical mixtures. Use this solution. and stored under nitrogen.

In the second method, while controlling the temperature of the phenolacetone solution to below 30°C, Thiophosphoryl bromide was mixed with a bromine container. The reactant ratio is 1:5.2:L0 5 to 1.09 (W/w/w phenol/bromine/bromide), which is Tripromol thiophosphate ester (70-80%) and the remainder is dibrothiophosphate. A mixture of mole esters was produced. This solution was then added to the Phosphate ester solution (20:1 w/w phosphate ester/sulfite ester ) and an amount of organic base (triethylamine) to neutralize 85-95% of the remaining acid component. ) were mixed. The mixture was poured into water and the white coagulated precipitate was immediately separated.

The precipitate was then dried to reduce the moisture content to less than 5% W/W. Then the most 0 reactant ratio by replacing the final mixture with compound I/It/l approximately 1515/rubromide. L: 5.2:0°94-0.97. The final mixture was then converted to compound III. / lv/v (approximately 1515/1).

A suitable additive is compound 1. Mixture A consisting of II and V (approximately 1515 /1. ). Compound V may be 3-12% of the mixture. In other words, 5% is the maximum deemed appropriate. Although triethylamine is flammable, it is a suitable neutralizing base; In some cases, it evaporates within 1 to 2 days.

When added to the isocyanate as provided herein, Mixture A contains the compound The greatest benefit has not yet been found from the use of any one of I can do it. This is based on the opinion of those who have studied the combustion of polyurethane foam, which is the object of the present invention. This evaluation is subjective, as shown in the table below that lists the consensus, but the inventor An up-to-date indication of the lack of several objective measurements important for carrying out this evaluation regarded as.

A similar mixture, ie mixture B, was prepared with compound I11. IV and V Contain and form.

The three types of forms listed in the table below do not exhibit significant physical differences. K-type Huo The choice of additive composition for the flame is a relatively important consideration of cost, flame retardation, and smoke suppression. as well as other physical properties imparted to the foam by additives. These other physical properties and (1) tend to improve cell structure and reduce or eliminate the need for silicone; (2) increased surface activity of the isocyanate prepolymer, (2) addition of silica sand cone; improved adhesion to the substrate expected from reduced (3) reduced need for polymerization catalyst; and (4) embrittlement and catastrophic loss caused by normal or premature aging. including the expected significant reduction in loss. Compounds superior to Compound III and TV in terms of solubility and solubility, but flammable, continuous It is inferior in terms of stability against chemical reactions and cost. Compound V burns itself and smoke suppressants, but in order to provide long-term stability in its application. It is primarily used as an antioxidant in combination with other compounds. of each of these compounds. The effect seems to be proportional to its content.

Table, polyurethane foam Relative performance of compositions Characteristics S type, G type, K type 1) Combustion retardation - Initial combustion 10) 20 > 4 One sustained combustion 10 1 3 2) Smoke from combustion Monocarbon 10)2o)3 One stimulus 10 1 3 3) Integrity after combustion Single cell structure 10) 20 > 20 > 8 - Collapse, crack 10 13 6 and delamination Total 60 27 22 S type: Bayer Dasmodur, : L -/l/ (Bayer Dasmodur ) 44V20 + Bayertherm 4150 (1: 1v/v), G type: Lackfa LamoItan ), Type K: Bayer Desmodur 44V20: Mixture A (100:16 W /W) + Bayer Team 4150 (1: IV/V) Mixture B was carried out in the same manner based on the above premise.

The table contains attachments all intended to reduce flammability and smoke ratings. Observations made after use and combustion of polyurethanes of various formulations are summarized. This way This form is the most difficult to minimize combustion effects. this The greatest characteristic of these, namely their insulation properties, is mainly due to their excessive insulation ability, which is extremely high during heating. Simultaneously for reasons that cause point temperature Their biggest drawback is their flammability. S form is standard Yes, it is a commonly sold type of injection form. This is polyurethane foam Tris(chloroerthyl) phosphate, a commonly used type of flame retardant Contains.

The G form is a different type of flame retardant that exhibits greater effectiveness than the S form. That is, a premium performance foam containing polybromophenyl ester. K type The foam is of the standard S type, modified only by the addition of the additives of the invention. subordinate Therefore, the table provides a direct comparison between those provided here and commercially available standard and premium forms. Show comparison.

The value for type S shall not be arbitrarily set to 10. That is, the optimal performance is zero. subordinate A low value is preferable. Both the G and Ni types work significantly better than the S type. Ru. Regarding combustion and smoke production, the K type is superior to the G type, but its overall performance is lower than the G type. In terms of structural integrity, which is significantly better than type K, type K is much better than type G. I want to. Type K ignites at a substantially lower temperature than the other two types. This is below intentionally for good reasons. In other words, low combustion temperature means (1) relatively low combustion temperature; (2) speed of fire spread and explosive fireball formation; and (3) polyurethane and other polymer fire hazards. Minimize the production of carbon monoxide, a major cause of death. Ni-type charcoal grilling is better than S-type charcoal grilling. The most significant advancements in type have been in the much less dramatic but widespread use of powerful Relatively likely to produce gaseous products recognized to be lethal be sure that it is low. Polyhalogenated as used in G type The use of diaryl esters is due to the fact that the compounds are known to be precursors of dioxins. have been voluntarily restrained from making any pending valid changes because they are suspected of being . Additives of the type provided herein are likely to persist in the K-type form. Demonstrates an inherent ability to produce dioxane even at the temperatures expected for combustion. do not have.

The invention provided herein provides a means for applying polyurethane to areas where it is most impeded due to its flammability. This has made significant progress in the applicability of the information format. The invention also includes Rather, it offers materials with surface-active and plastic properties that are important for a variety of key applications. provide

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Claims (24)

[Claims] 1. Equation XI of combustion delay amount: ▲There are mathematical formulas, chemical formulas, tables, etc.▼Compound XI and Formula XII: ▲There are mathematical formulas, chemical formulas, tables, etc.▼Compound XII (However, X1 and X2 are oxygen or sulfur, and RO- is 2,4,6-tribromophenoxy group) Polyurethane foam containing a mixture of. 2. Claim 1, wherein X1 and X2 are both oxygen or sulfur. form. 3. 3. The foam of claim 2, wherein X1 and X2 are both sulfur. 4. 3. The foam of claim 2, wherein XI and X2 are both oxygen. 5. Formula V: ▲There are mathematical formulas, chemical formulas, tables, etc.▼V (However, RO- is 2,4,6-tribromophenyl group) A foam according to any one of the preceding claims containing. 6. Equation XI of the amount of combustion retardation with respect to the foam that can be produced: ▲Mathematical formula, chemical formula, table, etc. There are ▼ compounds of XI and Formula XII: ▲There are mathematical formulas, chemical formulas, tables, etc.▼Compound XII (However, X1 and X2 are oxygen or sulfur, and RO- is 2,4,6-tribromophenoxy group) A polyurethane foam prepolymer containing a mixture of. 7. Claim 6, wherein X1 and X2 are both oxygen or sulfur. Prepolymer. 8. A prepolymer according to claim 7, wherein X1 and X2 are both sulfur. -. 9. A prepolymer according to claim 7, wherein X1 and X2 are both oxygen. -. 10. Formula V: ▲There are mathematical formulas, chemical formulas, tables, etc.▼V (However, RO- is 2,4,6-tribromophenyl group) The prepolymer according to any one of claims 6 to 9, comprising: 11. Claims 6 to 10, wherein the prepolymer is an isocyanate. The prepolymer according to any one of . 12. Claims 6 to 11, wherein the prepolymer is a polyol. Prepolymer according to any one of the above. 13. Any one of claims 6 to 12 further containing an organic base. Prepolymers described in. 14. Organic bases include triethyamine, ethylenediamine and triethanolamine. 14. The prepolymer of claim 13 selected from amines. 15. The compound of formula XI is present in the mixture in an amount of about 70 to 80% by weight. A prepolymer according to any one of ranges 6 to 14. 16. Claims that the compound of formula XII is present in the mixture in an amount of about 20 to 30% by weight The prepolymer according to any one of the ranges 6 to 14. 17. The compound of formula XIII is present in the mixture in an amount of about 3 to 8% by weight. Prepolymer according to scope 10. 18. The mixture contains about 2 (1/2) to 20% by weight, preferably about 8 to 10% by weight. According to any one of claims 6 to 17 present in the prepolymer. Prepolymers listed above. 19. Claim 13, wherein the organic base is present in the mixture in an amount of about 6 to 8% by weight. Prepolymers described in. 20. Formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼II (However, RO- is 2,4,6-tribro mophenyl group). 21. A compound of formula XI as defined in claim 1 and a compound of formula XI as defined in claim 1 A mixture consisting of a compound of formula XII. 22. Claim No. 5 further comprising a compound of formula V according to Claim No. 5 A compound according to item 21. 23. A foam, prepolymer, substantially as previously described with respect to any one of the embodiments. mer and mixtures. 24. Individually or collectively referred to in the specification and/or claims. or indicated articles, objects, parts, elements, steps, properties, methods, preparations, compounds and Any or all combinations of compositions and any two or more.