TWI512015B - Cross - linked polysiloxane molecules - Google Patents

Description

Crosslinked polyoxyalkylene molecule

The present invention relates to a polymer having cross-linking properties, in particular to a polysiloxanes molecule having a benzooxazine reactive group, thereby enhancing polyoxaxane Compatibility with other polymers.

It is known that polysiloxane is obtained by hydrolyzing cerium chloride as a raw material, and its long chain of molecules is composed of argon and oxygen atoms alternately, and there are many organic molecular groups around it, so that it has both organic and inorganic properties. The material is characterized by excellent heat resistance, low temperature resistance, weather resistance, ozone resistance, solvent resistance, electrical insulation, hydrophobicity and permeability due to its low glass-rubber transfer temperature (Tg). It has special mechanical and electrical properties under a wide range of temperature conditions, so it is used in commercial and military applications. Because it is not compatible with most organic polymers, it is widely used as a release agent for plastics, rubber, glass and metal. It is also used as defoamer, lubricant and polish.

The modification of polymer materials is generally carried out by adding a small amount of rubber to the plastic in a manner of blending or copolymerization. It is often used as a modifier for phenolic resins, acrylic resins and epoxy resins, but it is difficult to modify due to poor compatibility of polyoxyalkylene with other polymers and differences in polymerization.

According to the polyoxyalkylene polymer, a cross-linking reaction can be carried out by adding a hardener to form a crosslinked polymer having a three-dimensional structure, for example, a polyoxyalkylene having a hydrogen bond. Cross-linking with an addition reaction with a non-saturated bond, or crosslinking of a polyoxyalkylene polymer by adding a crosslinking agent capable of generating a radical, but the cross-linking reaction composition of the two dosage forms is controlled in application and properties. In terms of aspects, there are deficiencies. Therefore, the development of polyoxane molecules having self-crosslinking reaction characteristics is novel and progressive.

Further, the benzooxazine group can be self-polymerized by a ring-opening addition reaction, thereby reacting the oxo-nitrobenzocyclohexane group onto the polymer chain, that is, The polymer can be made into a self-crosslinkable polymer. Further, oxo-nitrobenzocyclohexane can be cured without generating volatile by-products upon heating, and is excellent in heat resistance, flame retardancy, and electrical properties, and is used for electronic materials such as laminates, adhesives, and encapsulants. Therefore, many molecules which combine the structure of oxoazobenzocyclohexane and a decane structure are synthesized, and these molecules are generally polyoxyxane having an oxoazobenzocyclohexane group at both ends. Molecules, which utilize the properties of a polyoxyalkylene molecular chain to improve the properties of an oxo-nitrobenzocyclohexane polymer, or to synthesize a polymer chain having a polyoxyalkylene repeating unit with a backbone An oxo-nitrobenzocyclohexane group to improve the brittleness of such polymers after crosslinking. Thus, the prior art largely utilizes polyoxyalkylene to improve the properties of oxo-benzobenzocyclohexane-based polymers which are originally thermosetting resins, rather than developing self-crosslinking reaction characteristics having novel structures and properties. Polyoxane.

In view of the above disadvantages of the prior art, the present invention provides a cross-linking polyoxyalkylene molecule having a polyoxymethane molecule as a main chain and an oxo-nitrobenzocyclohexane group as a chemical bond. Connecting to the pendant group of the polyoxyalkylene molecule to form a polyoxyalkylene molecule having a oxoazobenzocyclohexane group, wherein the oxobenzobenzocyclohexane is contained The group base increases the compatibility between the polyaluminoxane polymer and the general organic polymer material, oxo-nitrobenzocyclohexane The alkane group can also be self-polymerized by a ring-opening addition reaction to become a self-crosslinking polymer chain.

In the present invention, by adjusting the chain length of the oxirane chain, the functionality of the pendant group, and the cross-linking between the polymer chains, the oxirane can synthesize a myriad of materials, each of which has its own chemical properties and properties. By varying the type of organic functional groups attached to the ruthenium atom, a variety of compounds can be made to impart important organic properties, including compatibility and directivity. The oxirane is not compatible with organic polymers, but if a larger organic functional group is attached to the oxime, its properties will change and its performance will be close to that of the organic polymer; otherwise, it will be non-reactive. The oxane lacks directness. If a reactive organic functional group is attached to a hydrazine, the oxirane is reactive and forms a stable bond with other organic polymers.

The object of the present invention is to provide a cross-linked polyoxyalkylene molecule which is a polyoxyalkylene polymer chain having a oxo-nitrobenzocyclohexane group as a side group, and can also be cross-linked by itself. Reactive to obtain a cross-linked polyoxyalkylene polymer material, and because of the oxo-nitrobenzocyclohexane group contained, the compatibility between the polyaluminoxane polymer and the general organic polymer material is increased. The scope and feasibility of the large-scale use of polyoxyalkylene polymers for the adjustment of properties to organic polymeric materials. In addition, since the oxobenzobenzocyclohexane group can undergo a self-addition reaction, the reactive body generated during the ring-opening reaction is also reactive toward other chemical groups, for example, a phenol group, an amine group, a thiol group or the like, so that the polyoxyxane polymer having an oxoazobenzocyclohexane group group as a side group obtained by the present invention may also be a reactive reagent. It is added to other compounds or materials and chemically bonded to them to obtain crosslinked polymer materials.

A second object of the present invention is that the crosslinked polyoxyalkylene molecular system is a pendant group. A polyoxyalkylene polymer chain having an oxoazobenzocyclohexane group, the crosslinked structure produced by the ring-opening addition reaction of the oxonitrobenzocyclohexane group, in the pyrolysis In the process, it has the characteristics of high coke formation, and the high coke formation characteristics can effectively increase the amount of flammable substances released into the gas phase as a fuel in the thermal cracking process of the polymer material, and the solid phase resistance of the organic polymer material. On the other hand, organic bismuth has been proven to be effective in the formation of cerium oxide during thermal cracking, because cerium oxide moves to the surface of the material because of its lower surface energy. Moreover, because of its very high thermal stability, cerium oxide is not thermally cracked at normal flame temperatures, so it can be used as a protective layer for organic materials to prevent it from being thermally cracked, thus contributing effectively to the improvement of organic materials. Flame retardant properties. When this action acts together with the above-described mechanism having high coke formation characteristics, the synergistic effect can be exerted on the flame retardant effect, that is, the synergistic effect of the flame retardant effect is exerted.

The mechanism of the above thermal cracking to form a cerium oxide structure can be seen in a polyoxyalkylene having a phenyl group, but for a relatively low-cost and commonly used polydimethyl siloxane, the thermal cracking usually depends on the formation of dimethyl groups. A cyclic trimer or a cyclic tetramer of a decane is a cracking product, and the cleavage product is directly dispersed in a gas phase, and it is difficult to form a ceria-like cleavage product, and thus, polydimethyl oxime In the test of thermal cracking of the alkane polymer, it is impossible to form a heat-resistant composition similar to cerium oxide, and it is also difficult to exert the mechanism of improving the flame retardant effect as described above, that is, the polydimethyl siloxane polymer is relatively inexpensive. The convenient and easily available source of organic germanium is difficult to play an effective role in improving the combustion characteristics of organic polymer materials.

The polyadenine polymer with oxobenzobenzocyclohexane group on the side group disclosed in the present invention forms an open-loop structure of oxo-nitrobenzocyclohexane after ring-opening crosslinking reaction Concatenated and linked to the main chain structure of polydimethyl siloxane by chemical bonding, this structure can be In order to make the molecular chain of polydimethyl methoxyoxane interact with the oxo-nitrobenzoxene cross-linking structure formed by the ring-opening reaction during the thermal cracking, the polydimethyl group is effectively changed. A pyrolysis mechanism in which a sulfoxane is produced as a cracked product by a cyclic trimer or a cyclic tetramer, and the cracked product is directly dispersed in a gas phase. That is, a polyaluminoxane polymer having a oxoazobenzocyclohexane group on the side group, a crosslinked body formed after the ring-opening crosslinking reaction, and a molecular chain of polydimethyloxane When pyrolysis is carried out, the characteristics of coke formation are exhibited, and the helium oxygen structure can be left in the generated coke to be converted into a highly heat-resistant cerium oxide-like substance, which plays a role in the flame-retardant effect.

The present invention provides a polyoxyalkylene polymer having an oxonitrobenzocyclohexane reaction group, which is a polyaluminoxane polymer capable of self-crosslinking reaction, which can react with itself or with other materials. Obtaining a cross-linked polymer material; further, the polyoxyaphthene polymer having an oxo-nitrobenzocyclohexane group-based group, in the presence of an oxo-nitrobenzocyclohexane group, can increase the polyfluorene The coke formation rate of the oxyalkylene polymer in the thermal cracking process can be applied as a flame retardant for increasing the flame retardant effect of the polymer material.

The embodiments of the present invention are described below by way of specific examples, and those skilled in the art can readily appreciate the other advantages and advantages of the present invention.

The present invention provides a polyfluorene oxide molecule having a cross-linking polyoxyalkylene molecule having a oxo-nitrobenzocyclohexane group as a pendant group. In order to thoroughly understand the present invention, the following The structure and its components and method steps are presented in the description. Obviously, the implementation of the present invention is not Particular details that are well-known to those skilled in the art of cross-linking polymers, oxobenzobenzocyclohexane molecules and their polymers, polyoxyalkylenes. On the other hand, well-known structures and elements thereof are not described in detail to avoid unnecessary limitation of the invention.

Embodiment 1

Please refer to Equation 1 and use the polyoxyalkylene molecular chain (1) with Si-H chemical group in the repeating unit. The number and proportion of Si-H chemical groups contained in the repeating unit are not limited, but cross-linking is considered. The reaction and the structure of the obtained crosslinked product, the proportion of the Si-H group in the repeating unit in the polyoxyalkylene molecular chain is preferably from 0.03 to 2.0. The reaction of the compound 1 with 2-hydroxybenzaldehyde or a derivative thereof (2) is carried out by subjecting the C=O group of the aldehyde group of the compound 2 to an addition reaction through the Si-H group to form the reactant 2 The Si-C chemical bond reaction is carried out on the molecular side group of the reactant 1, and the formed reaction product 3 is subjected to ring closure reaction with formaldehyde or its derivative (4), and oxonitrobenzene is formed in the polyoxyalkylene molecular chain. And a pendant group of cyclohexane, which produces a polyoxyalkylene molecular chain having a oxoazobenzocyclohexane group as a side product. This formula represents an example of the production method, and does not limit the reaction raw materials used in the production method and the structure and type of the produced product. The above two reaction steps may be carried out separately, or in the case where the compound 3 is not isolated, the product 5 is directly produced from the raw material 1 in a one-pot, two-step reaction.

Embodiment 2

Please refer to Equation 2, using the polyoxyalkylene molecular chain (6) with a primary amine (-NH ₂ ) pendant group in the repeat unit, which contains the number and proportion of the primary amine (-NH ₂ ) pendant group Without limitation, considering the cross-linking reaction and the structure of the obtained cross-linked product, the proportion of the number of primary amine (-NH ₂ ) side group chemical groups in the repeating unit in the polyoxyalkylene molecular chain is 0.03- 2.0 is better. The reaction is carried out using phenol or a derivative thereof (7) and formaldehyde or a derivative thereof (4), and the reaction is carried out by a conventional reaction for producing oxoazobenzocyclohexane, in a polyoxyalkylene oxide. The molecular chain forms a pendant group of oxoazobenzocyclohexane, which produces a polyoxyalkylene molecular chain (8) having a oxoazobenzocyclohexane group on its side. This formula represents an example of the production method, and does not limit the reaction raw materials used in the production method and the structure and type of the produced product.

Embodiment 3

Please refer to Equation 3, using a polyoxyalkylene molecular chain (9) with a phenolic group (-PhOH) or a pendant group derived from a chemical group in a repeating unit, which contains a phenol group or a chemical derived therefrom. The number and proportion of the group are not limited. However, considering the cross-linking reaction and the structure of the obtained cross-linked product, the number of phenol groups or the number of chemical groups derived therefrom is in the repeating unit in the molecular chain of the polyoxyalkylene. The ratio is preferably 0.03-2.0. An aromatic or aliphatic compound having a primary amine functional group or a derivative thereof (10) and formaldehyde or a derivative thereof (4) are reacted with a compound 9 by a conventional generation of oxonitrobenzene The reaction of cyclohexane is carried out to form a pendant group of oxo-nitrobenzoxanone in the molecular chain of the polyoxyalkylene to produce a polyoxyalkylene molecule having a oxoazobenzocyclohexane group in the pendant group. Chain (11). This formula represents an example of the production method, and does not limit the reaction raw materials used in the production method and the structure and type of the produced product.

Embodiment 4

Referring to Equation 4, a polyoxyalkylene molecular chain (12) having a pendant group having a reactive group in the repeating unit may be used. The reactive group may be the aforementioned Si-H, phenol group, amine group, or Other reactive groups such as aldehyde groups, ketone groups, epoxy groups, acid groups, ester groups, polyunsaturated groups, or other chemical groups which can undergo addition or condensation reactions, and reactivity The group-based oxoazobenzocyclohexane compound (13) is reacted, wherein 13 reactive groups and 12 reactive groups can be added or condensed, and The structure of 12 oxo-nitrobenzoxanene is attached to the pendant group of the polyoxyalkylene molecular chain, and the number and proportion of the oxo-nitrobenzocyclohexane structure of the pendant group are not limited, The cross-linking reaction and the structure of the obtained cross-linked product are considered, and the proportion in the repeating unit in the polyoxyalkylene molecular chain is preferably from 0.03 to 2.0. The reaction is carried out by a conventional polymer reaction to form a pendant group of oxoazobenzocyclohexane in the molecular chain of the polyoxyalkylene to produce a polyfluorene having an oxoazobenzocyclohexane group. Oxytomane molecular chain (14). This formula represents an example of the production method, and does not limit the reaction raw materials used in the production method and the structure and type of the produced product.

Embodiment 5

The polyoxosiloxane molecular chain of the oxo-nitrobenzocyclohexane group of the present invention can be subjected to a self-crosslinking reaction, and the compound 5 obtained in the first embodiment is heated at 130 ° C for 1 hour and heated at 150 ° C. After heating at 190 ° C for 1 hour at 1 hour, a crosslinked polyaluminoxane polymer was obtained, which showed a high coke formation rate compared to the original polyoxyalkylene raw material.

The above-described embodiments are merely illustrative of the features and functions of the present invention and are not intended to limit the scope of the technical scope of the present invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention should be as set forth in the scope of the claims described below.

Claims (9)

A cross-linked polyoxyalkylene molecule having a structure comprising the following chemical formula, Wherein 500 ≧ x + y ≧ 2, at least one of the substituents R 1 or R 2 carries a oxo-nitrobenzocyclohexane-based molecule. The crosslinked polyoxyalkylene molecule according to claim 1, wherein the substituent is obtained by reacting a hydrogen group-containing polyoxyalkylene molecule with 2-hydroxybenzaldehyde or a derivative thereof. Further, a ring-closing reaction with formaldehyde or a derivative thereof is carried out to form a polyoxyalkylene molecule having a pendant oxoazobenzocyclohexane structure. The cross-linked polyoxyalkylene molecule according to claim 1, wherein the substituent is derived from a phenol-containing polyoxyalkylene molecule, a primary amine functional aromatic or aliphatic compound or a derivative thereof. The reaction with formaldehyde or a derivative thereof to form oxoazobenzocyclohexane forms a polyoxyalkylene molecule having a pendant oxobenzobenzocyclohexane structure. The crosslinked polyoxyalkylene molecule according to claim 1, wherein the substituent is composed of a phenol group, an amine group, an aldehyde group, a ketone group, an epoxy group, an acid group, an ester group, and a multi bond. An unsaturated group or a chemical group-based polyoxyalkylene molecule capable of undergoing addition or condensation reaction with an oxoazobenzocyclohexane compound having a reactive group to form a pendant oxo-nitrobenzene And a polyoxane molecule of a cyclohexane structure. The crosslinked polyoxyalkylene molecule according to claim 1, wherein the methyl group on the germanium atom of the polyoxyalkylene may also be an aliphatic group having 2 to 12 carbon atoms or It is an aromatic group. The crosslinked polyoxyalkylene molecule according to claim 1 or 5, wherein the substituent R ₁ or R ₂ may be a molecule containing 1 oxoazobenzocyclohexane group, or The self-linking has two or more oxo-nitrobenzocyclohexane-based molecules. The cross-linked polyoxyalkylene molecule according to claim 6, wherein the number of the oxo-nitrobenzocyclohexane group-based molecules is 0.03-2.0 in a ratio of the number of repeating units x+y. The cross-linked polyoxyalkylene molecule according to claim 1, wherein the molecule is a flame retardant for a polymer material. The cross-linked polyoxyalkylene molecule according to claim 1, wherein the molecule is a reactive additive for a polymer material.