KR830002061B1 - Method for preparing a polymer polymer having a crosslinked structure - Google Patents

Abstract

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Description

Method for preparing a polymer polymer having a crosslinked structure

The present invention relates to a method for producing a polymer polymer having a new social structure.

More specifically, the formula in the molecule

It relates to a method for producing a polymer cross-linked polymer having a novel cross-linked structure, characterized in that a specific oxazoline (Oxazoline) derivative is reacted with a polymer having a partial structure represented by.

In general, the polymer polymer having no crosslinked structure can be used as a solution or fluidized by heating, which is advantageous in operation, but also has a drawback in that solvent resistance and heat resistance are not sufficient. Therefore, it is meaningful to give these polymer polymers which do not have a crosslinked structure with an appropriate degree of crosslinked structure and to improve their physical properties.

The present invention has been studied in view of such circumstances, and as a result, by using a specific oxazoline derivative as a crosslinking agent, the object has been achieved and the present invention has been completed.

In other words, the present invention is formulated in the molecule

Polymeric polymer having a partial structure represented by the general formula

(Wherein n is an integer of 1 to 4, R is an n-valent aromatic hydrocarbon residue, (, R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and are hydrogen or 3 carbon atoms) The following hydrocarbons are represented.) An oxazoline derivative represented by the present invention is reacted.

Formula in the molecule used in the present invention

The polymer polymer having a partial structure represented by may be any polymer polymer having at least one partial structure in the main chain or the side chain. Typically, maleic anhydride, citraconic anhydride, itaconic anhydride and the like are obtained by copolymerizing a synthetic monomer having one or two or more vinyl groups by a known method. Moreover, it can also be obtained by graft-polymerizing the synthetic monomer which has maleic anhydride etc. and a vinyl group in the linear polymer compound obtained solely or by copolymerization of a polymerizable vinyl monomer.

The polymerizable monomer which has a vinyl group may be used normally, for example, styrene, chloro styrene, methyl styrene, ethylene, propylene, buradiene, bilylidene chloride, vinyl chloride, vinyl embrittlement, vinyl fluoride, vinyl acetate, vinyl propionate, Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate methyl methacrylate, triethyl acrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, vinyl pyridine, methyl vinyl ether Although ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, acrylamide, acrylic acid, methacrylic acid, maleic acid, and iraconic acid are used suitably, it is not limited to these.

Formula in Raw Material Polymer Polymer in the Present Invention

Although the content rate of the partial structure represented by is not restrict | limited, The thing of the range of 0.5-50 weight% is preferable. When the degree of crosslinking of the polymer polymer having a crosslinked structure to be obtained is desired to be high, the content rate of the group represented by this partial structure is increased, and when the degree of crosslinking is not required very much, it can be reduced. However, since the crosslinking effect may not be exhibited when the content rate of this partial structure in a polymer is 0.5% or less, it is preferable to contain 0.5% or more.

The oxazoline derivative used in the present invention is a compound represented by the following general formula in the Δ ² -oxazoline derivative having an aromatic substituent thereon.

R: n-valent aromatic hydrocarbon residue

R ₁ to R ₄ : H or hydrocarbon group having 3 or less carbon atoms

n is an integer from 1 to 4

The compound represented by the said Formula is shown concretely.

Bis of the above compound is obtained in the - (Δ ² oxazolidone carbonyl-2) benzenes can be easily and conveniently used.

The ratio of use of the polymer structure having the partial structure and the oxazoline derivative can be arbitrarily selected. However, in the case where a particularly rigid crosslinking is required, the oxazoline ring in the oxazoline derivative is used for one of the partial solids in the polymer polymer. ) Is preferably 1.5 to 3.0.

When the 2-aromatic substituted Δ ² -oxazoline compound is used as the crosslinking agent as in the present invention, the reaction is milder than when the ² -aliphatic substituted Δ ² -oxazoline compound is used, for example, and the raw polymer polymer and the oxazoline derivative are used. In the case of mixing, it has the advantage that the pot life is long and that the colorability of the mixture and the cured product is slight.

The crosslinking reaction is carried out at room temperature or under heating, and the higher the temperature, the shorter the time is, but the treatment is usually performed at room temperature to 200 ° C. When using for a coating material and an adhesive agent, you may use the organic solvent as needed. Examples of organic solvents that can be used include methyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl glycol acetate, tetrahydrofuran, dioxane, ethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Benzene, toluene, xylene, dimethylformamide, dimethylacetoamide, chloroform, carbon tetrachloride, methylene chloride, and the like. If necessary, preparations, fillers, and leveling agents ), Surfactant, village, pigment, dye and the like can be added. In addition, maleic anhydride, amber anhydride, or the like may be added as necessary.

The polymer crosslinked polymer having the new crosslinked structure thus obtained has excellent adhesiveness and is of high industrial value as a pigment, an adhesive, and a molded article with further improved heat resistance solvent resistance.

Example 1

Maleic anhydride and 1 part of 40% of the vinyl chloride polymer obtained 99 parts by polymerizing butyl acetate polymer solution and 35g of 1,3-bis-mixing and dissolving the (Δ ² oxazolidone carbonyl-2) benzene and 0.3g was applied on the cold glass . Varnish's port life was five days. After seven days, the varnish was pale yellow gel and the coating was colorless and transparent. Further, ethyl acetate was dropped on the coating film, and the dissolved state of the coating film was observed. The coating film swelled but did not dissolve. For comparison, the same operation was performed on the coated membrane without adding the oxazoline compound, and the coating film was dissolved.

Example 2

Vinyl acetate, 30 parts ethylene and 70 parts of a copolymer of maleic anhydride 2.2 parts of styrene 2.8 to 20% of the high molecular polymer obtained by the graft portion of a toluene solution with 30g of 1,3-bis-a (Δ ² oxazolidone carbonyl-2) benzene first The amounts shown in the table were mixed and dissolved, and the glass and the tin plate, the glass and the aluminum foil were bonded together, and after 7 days, the heat-resistant test, the test, and the 180 ° peeling test were performed (Table 1).

In particular, heat resistance was greatly improved.

[Table 1]

* The number of days until no flow

** Temperature at which the adhesive softens and the adhesive peels

*** 180 ° peeling

Example 3

Solvent solution for mixing ethyl acetate and toluene (70% ethyl acetate, 30% toluene) of a polymer polymer obtained by polymerizing 70 parts of vinyl chloride, 30 parts of vinyl acetate, and 1.5 parts of maleic anhydride (14 g of 50% solids and 1,3-bis) Δ ² - mixture of benzene was dissolved 0.22g oxazolidone carbonyl-2), and by bonding the glass and the amount of iron had a heat resistance test of 7 days after the bonding.

[Table 2]

* 1,3-bis (Δ ² -oxazolinyl-2) benzene is not added

Example 4

Toluene, butyl acetate, acetone (mixing ratio 1: 1: 1) 12.5 g of mixed solvent solution (solid content 40%) and 1,3- bis (Δ ² - oxazolidone carbonyl-2) mixing and dissolving 0.55g of benzene, and investigated the change in the solution. Reaction was gradually carried out, and a small amount of gelled material was precipitated, and the amount of gelled material increased with the progress of the date. After 7 days, the polymer became gel and precipitated in the lower layer, and the solvent was separated in the upper layer. It was confirmed that the gelled material was insoluble in a solvent and was a crosslinked polymer.

Comparative Example 1

Example 1 40% of the high molecular polymer with a butyl acetate solution, and 35g of 1,4-bis (Δ ² - oxazolidone carbonyl-2) mixing and dissolving the butane 0.15g, and was coated on a glass plate. After seven days, the varnish became a brown gel, and the coating was cloudy and opaque and transparent, which could not be provided for practical use. Also, the varnish's port life was about a day.

Comparative Example 2

35 g of 40% butyl acetate solution and 0.15 g of ² -ethyl-Δ2-oxazoline of the polymer polymer used in Example 1 were dissolved and coated on a glass plate. After 7 days, the varnish had a dark brown color, and the coating was yellowish and slightly cloudy.

Claims (1)

Intramolecular formulas as described above in the text

Polymeric polymers having a partial structure represented by

Method for producing a polymer polymer having a crosslinked structure, characterized in that for reacting the oxazoline derivative represented by. (Wherein n is an integer of 1 to 4, R is an n-valent aromatic hydrocarbon residue, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and represent hydrogen or a hydrocarbon group having 3 or less carbon atoms).