JPH0441683B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing a polymer having acylisocyanate groups. BACKGROUND OF THE INVENTION Compounds having isocyanate groups are widely used in the field of polymer chemistry because of their excellent reactivity. In particular, compounds that have both a polymerizable carbon-carbon unsaturated group and an isocyanate group in the same molecule are used in a wide range of industrial technology fields because both functional groups participate in various reactions with different reaction mechanisms. It can be used. Focusing on such usefulness, the present inventors previously provided an isocyanate compound represented by the following formula [Patent Application No. 1983-
No. 225226]: [In the formula, R represents a lower alkyl group] Furthermore, an acylisocyanate group-containing polymer obtained by polymerizing this isocyanate compound was also provided. This acyl isocyanate group

[Formula] has a carbonyl group adjacent to the isocyanate group, and this carbonyl group increases the activity of the isocyanate group and is in a state where it can carry out a wide variety of addition reactions. Therefore, the polymers potentially have a wide range of applications. (Object of the Invention) The object of the present invention is to provide a new method for producing the above-mentioned polymer, that is, a polymer having an acylisocyanate group. (Structure of the invention) That is, the present invention has the formula: [wherein R is hydrogen or lower alkyl (e.g.
methyl, ethyl, propyl group, etc.), X represents an acid residue (eg, halogen, especially chlorine). ] Carbon-carbon characterized by thermally decomposing 2-(α-alkyl)vinyloxazoline-4,5-dionic acid salt ( ) represented by and then polymerizing it alone or with other monomers not having active hydrogen. The main chain consisting of bonds contains acyl isocyanate groups from 0.1 to
Provided is a method for producing a polymer containing 1000 to 100,000 acylisocyanate groups combined in an amount of 72.2% by weight. In addition, the present invention has a main chain consisting of carbon-carbon bonds with the formula: [In the formula, X has the same meaning as above. ] Reactive oxazolinedione ring ()
is characterized in that it thermally decomposes a polymer having reactive oxazolinedione rings attached in an amount of 0.1 to 83.3% by weight, characterized in that the main chain consisting of carbon-carbon bonds has acylisocyanate groups in an amount of 0.1 to 72.2% by weight. A method for producing a polymer containing bonded acylisocyanate groups with a molecular weight of 1,000 to 100,000 is provided. By reacting methacrylamide and oxalyl chloride under specific conditions, the formula: 2-isopropenyl-osisazoline- with
The fact that 4,5-dione hydrochloride can be obtained is from Die Macromolecule Chemie.
Makromolekulare Chemie) 141 (1970) 247~
257 (No. 3199) by Von H. Diefenbath and H. Ringsdorf. 2-(α-alkyl)vinyloxazoline-4,
By thermal decomposition, e.g. heating at a temperature above 40°C, the 5-dionic acid salt () can be converted to the formula: A mixture of two compounds having . The target polymer of the present invention is usually obtained by polymerizing this compound (). Actually the compound (),
That is, without isolating the α-alkyl acryloyl isocyanate, it is polymerized as a mixture with the compound (). The polymerization may be carried out with the compound () alone to obtain a homopolymer, or it may be polymerized with another ethylenically unsaturated monomer having no active hydrogen to obtain a copolymer. Monomers having active hydrogen cannot be used because they react with isocyanate groups. Examples of ethylenically unsaturated monomers without active hydrogen include monoolefins and olefin hydrocarbons, i.e. monomers having only hydrogen and carbon atoms, such as styrene, α-methylstyrene, α-ethylenestyrene, Isobutylene (2-methyl-propane-1), 2-methyl-butene-1, 2-ethylene-pentene-1,2,3-
dimethyl-butene-1, 2,3-dimethyl-pentene-1, 2,4-dimethyl-pentene-1,
2,3,3-trimethyl-heptene-1,2,
3-dimethyl-hexene-1, 2,4-dimethyl-hexene-1, 2,5-dimethyl-hexene-
1,2-methyl-3-ethyl-pentene-1,
2,3,3-trimethyl-pentene-1,2,
3,4-trimethyl-pentene-1, 2-methyl-octene-1, 2,6-dimethyl-heptene-
1,2,6-dimethyl-octene-1,2,3-
Dimethyl-decene-1,2-methyl-nonadecene-1, ethylene, propylene, butylene, amylene, hexylene, butadiene-1,3, isoprene, etc.; halogenated monoolefin and diolefin hydrocarbons, i.e. carbon atoms, hydrogen atoms and 1
Monomers having halogen atoms or more, e.g.
α-chlorostyrene, α-bromostyrene, 2,
5-dichlorostyrene, 2,5-dibromostyrene, 3,4-dichlorostyrene, ortho, meta and para-fluorostyrene, 2,6-dichlorostyrene, 2,6-difluorostyrene, 3-fluoro-4-chlorostyrene , 3-chloro-4-
Fluorostyrene, 2,4,5-trichlorostyrene, dichloromonofluorostyrene, 2-chloropropene, 2-chlorobutene, 2-chloropentene, 2-chlorohexene, 2-chloroheptene, 2-bromobutene, 2-bromoheptene, 2
-fluorohexene, 2-fluorobutene, 2-
Iodopropene, 2-iodopentene, 4-bromoheptene, 4-chloroheptene, 4-fluoroheptene, cis- and trans-1,2-dichloroethylene, 1,2-dibromoethylene, 1,2
-difluoroethylene, 1,2-diiodoethylene, chloroethylene (vinyl chloride), 1,1
-dichloroethylene (vinylidene glolide),
Bromoethylene, fluoroethylene, iodoethylene, 1,1-dibromoethylene, 1,1-difluoroethylene, 1,1-diiodoethylene,
1,1,2-trifluoroethylene, chlorobutadiene and other halogenated diolefin compounds; esters of organic and inorganic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate; vinyl caproate, vinyl enanthate, vinyl benzoate, vinyl toluate, vinyl-p-chlorobenzoate, vinyl-o-chlorobenzoate and similar vinyl halobenzoates, vinyl-p-methoxybenzoate,
Vinyl-p-ethoxybenzoate, methyl methacrylate, ethylene methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, methyl crotonate and ethyl tiglate; methyl acrylate, ethyl acrylate, propyl acrylate , isopropyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, octyl acrylate, 3,5,
5-trimethylhexyl acrylate, decyl acrylate and dodecyl acrylate; isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl valerate, isopropenyl caproate, isopropenyl enanthate, isopropenyl propenyl benzoate, isouropenyl-p-chlorobenzoate,
Isopropenyl-o-chlorobenzoate, isopropenyl-o-bromobenzoate, isopropenyl-m-chlorobenzoate, isopropenyl toluate, isopropenyl-α-chloroacetate and isopropenyl-α-bromopropionate; vinyl-α -chloroacetate, vinyl-α-
Bromoacetate, vinyl-α-chloropropionate, vinyl-α-bromopropionate, vinyl-α-iodopropionate, vinyl-α-
Chlorobutyrate, vinyl-α-chlorovalerate and vinyl-α-bromovalerate; allyl chloride, allyl cyanide, allyl bromide, allyl fluoride, allyl iodide, allyl chloride carbonate, allyl nitrate, allyl thiocyanate, allyl formate , allyl acetate, acetate propionate, allyl butyrate, allyl valerate, allyl caproate, allyl-3,5,5-trimethylhexoate, allyl benzoate, allyl acrylate, allyl crotonate, allyl oleate, allyl Chloroacetate, allyl trichloroacetate, allyl chloropropionate, allyl chlorovalerate, allyl lactate, allyl pyruvate, allyl aminoacetate, allyl acetoacetate, allyl thioacetate, methallyl esters corresponding to these allyl esters,
Also, β-ethyl allyl alcohol, β-propyl allyl alcohol, 1-buten-4-ol, 2
-Methyl-buten-4-ol, 2-(2,2-
esters derived from alkenyl alcohols such as dimethylpropyl)-1-buten-4-ol and 1-penten-4-ol; methyl-α-chloroacrylate, methyl-α
-bromoacrylate, methyl-α-fluoroacrylate, methyl-α-iodoacrylate,
Ethyl-α-chloroacrylate, Propyl-α
-chloroacrylate, isopropyl-α-bromoacrylate, amyl-α-chloroacrylate, decyl-α-chloroacrylate, methyl-
α-cyanoacrylate, ethyl-α-cyanoacrylate, amyl-α-cyanoacrylate and decyl-α-cyanoacrylate; dimethyl maleate, diethyl maleate, diallyl maleate, dimethyl fumarate, diethyl fumarate, dimethallyl fumarate esters and diethyl glutaconate; organic nitriles such as acrylonitrile,
methacrylonitrile, ethacrylonitrile, 3-
Octenitrile, crotonitrile, oleonitrile, etc. Polymerization is carried out by radical reaction in the presence of an inert solvent. Any solvent may be used in the polymerization reaction as long as it dissolves the reactants and products. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, benzene,
Aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin, hydrocarbon solvents such as petroleum ether and petroleum benzine, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbon solvents, ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, and tetrahydrofuran, acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
It can be appropriately selected and used from ketones such as cyclohexanone, acetophenone, and isophorone, esters such as ethyl acetate and butyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide, and the like. Usually, a radical catalyst is preferably used as a polymerization catalyst. For example, azobisisobutyronitrile,
benzoyl peroxide, cumene hydroperoxide,
Tetramethylthiuram disulfide, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), acetylcyclohexylsulfonyl peroxide, 2,2'-azobis(2,4-dimethylvaleronitrile), etc. The catalyst content is usually 0.1 to 10% by weight based on the amount of monomer.The polymerization temperature is usually 40 to 200°C, preferably 60 to 150°C.
It is ℃. During polymerization, other additives may be added as desired, such as
A polymerization regulator or the like may be added. The polymer obtained by the polymerization reaction has reactive acylisocyanate groups bonded to the carbon-carbon skeleton in a ratio of 0.1 to 72.2% by weight, preferably 5 to 72.2% by weight. The molecular weight of the polymer is usually 1,000 to 100,000. This polymer may be prepared by first thermally decomposing the compound () having a reactive oxazoindione ring and then carrying out the polymerization reaction, or by first polymerizing the compound () to form a reactive oxazoindione ring. It may also be obtained by forming a polymer having dione rings and then thermally decomposing this polymer. The polymerization reaction of compound () is carried out in substantially the same manner as described above. However, the polymerization temperature cannot exceed the temperature at which the reactive oxazolinedione ring decomposes. As a result of the polymerization reaction, the main chain consisting of carbon-carbon bonds has the formula: [In the formula, X represents an acid residue. ] Reactive oxazolinedione ring ()
A polymer having a reactive oxazolinedione ring bound in an amount of 0.1 to 83.3% by weight is obtained, and the desired product is obtained by thermally decomposing this in the same manner as described above. (Effect) As described above, the acyl isocyanate group increases the activity of the isocyanate due to the presence of the carbonyl group adjacent to the isocyanate group. Therefore, polymers with this acylisocyanate group easily interact with monomers or polymers with active hydrogen ( ¹⁰ times faster than isocyanate groups).
react. Therefore, it has great activity not only in modifying and modifying polymers, but also in crosslinking and grafting reactions.
It is particularly promising as a material for paints, adhesives (especially instant adhesives), plastics, elastomers, etc. (Example) The present invention will be explained with reference to an example. Example 1 Synthesis of copolymer from 2-isopropenyloxazoline-4,5-dione hydrochloride: A polymer was synthesized using the following recipe. Component weight parts (g) 2-isopropenyloxazoline-4,5-dine hydrochloride 15 Methyl methacrylate 20 n-butyl acrylate 15 V-65 ⁽¹⁾ 1.25 Ethyl acetate 25 Toluene 50 (1) Wako Pure Chemical Industries, Ltd. 2,2'-azobis(2,4-dimethylvaleronitrile) polymerization initiator commercially available from ). 2-isopropenyloxazoline-4,5-dione hydrochloride 15g, methyl methacrylate
20g, n-butyl acrylate 15g and V-56
(1.25g) was dissolved in 25g of ethyl acetate. The resulting solution was added to 50 g of toluene heated to 100° C. over 90 minutes with stirring. After stirring for 5 hours after dropping, a copolymer was obtained (non-volatile content (NV
= 40%), viscosity C- by Gardner bubble viscometer
D, IR spectrum: ν _NCO 2260 cm ⁻¹ ). 6.3 g of t-butyl alcohol was added to this copolymer to obtain a blocked isocyanate copolymer. The molecular weight of the copolymerization determined by gel permeation chromatography (GPC) was 7100. Example 2 Synthesis of homopolymers from oxazolinedione-containing polymers: Homopolymers of 2-isopropenyloxazoline-4,5-dione hydrochloride (Mn=
1800) in ethyl acetate solution (NV = 30%) from 70 to
An acylisocyanate group-containing homopolymer was obtained by heating and stirring at 80° C. for 1 hour. IR spectrum, ν _NCO ; 2260 cm ^-1 Gardner bubble viscosity: A-B Example 3 Synthesis of copolymers from oxazolinedione-containing polymers: Copolymer of 2-isopropenyloxazoline-4,5-dione hydrochloride (Mn = 4500) in ethyl acetate solution (NV = 40%) at 70-80℃.
The mixture was heated and stirred for hours to obtain an acylisocyanate group-containing copolymer. IR spectrum, ν _NCO ; 2260 cm ^-1 Gardner bubble viscosity: B Note that the starting material compound for the method of the present invention is given the chemical structure of the above formula () and is named based on this; It should be noted that while there are considerable reasons for assigning the formula () to the starting material compound of the method of the present invention, there are still some doubts regarding the same formula. That is, the chemical structure of formula () given to the starting material compound of the method of the present invention is derived from the above-cited document by Deiffenbach et al. Reaction products obtained by carrying out the same reaction using exactly the same raw materials (i.e., methacrylamide and oxalyl chloride) (for example, patent application filed in 1983-
¹ H-NMR of Specification No. 101726, Examples 2 to 7)
When the spectrum is examined in detail, the signal that Deiffenbatscha et al. attributed to vinyl protons appears around δ4.5 ppm, which tends to be shifted a little too high in the magnetic field. Moreover, the up-field shift of this signal hardly changes even if the measurement solvent is changed. Therefore, it is presumed that the shielding effect is due to some kind of shielding effect such as vinyl protons, but as long as the chemical structure of the above formula (:R=CH ₃ ; There is little possibility that it will occur. That is, the above formula (:R=CH ₃ ;X=
This is why there are doubts about the chemical structure of Cl). Therefore, when we attempted to analyze the reaction product using ¹³ C-NMR spectrum, we found that δ41.5ppm
A signal believed to be methylene carbon was observed at δ42.0ppm, and it was also observed that each signal appeared in pairs. Based on these facts, it has become possible that the reaction product is a mixture of substances with the following chemical structure: However, if the reaction product has such a chemical structure, the formula: Although it is thought that only α-methyl-β-chloropropionyl isocyanate shown by the formula is produced, in reality this and the formula: A mixture of methacryloyl isocyanates is obtained. In the chemical structure of formula ('), the chlorine atom is covalently bonded to the carbon atom, so it is difficult to imagine that the chlorine atom will be easily separated. Formula (:R=
CH ₃ ; X=Cl) if the chemical structure is HCl
Since it is bound as a salt, its elimination (that is, the elimination of the chlorine atom) should occur much more easily. Therefore, the reaction product has the formula (')
It is also not possible to immediately determine if it has the chemical structure. As described above, there are some doubts about the chemical structure of formula (), but since it is currently difficult to propose a chemical structure that is appropriate for each region, formula () will be adopted as is in this specification. I made it. However, no matter what chemical structural formula the starting material compound for the method of the present invention is represented by, substantially the same chemical substance is used, substantially the same reaction proceeds as in the method of the present invention, and the same chemical structure is obtained. It must be understood that as long as the results are obtained, the invention falls within the technical scope of the present invention.

Claims (1)

[Claims] 1 Formula: [In the formula, R represents hydrogen or lower alkyl, and X represents an acid residue. ] Carbon-carbon characterized by thermally decomposing 2-(α-alkyl)vinyloxazoline-4,5-dionic acid salt ( ) represented by and then polymerizing it alone or with other monomers not having active hydrogen. The main chain consisting of bonds contains acyl isocyanate groups from 0.1 to
A method for producing a polymer containing acylisocyanate groups with a molecular weight of 1000 to 100000 bound in an amount of 72.2% by weight. 2. The method according to item 1, wherein the thermal decomposition is carried out at a temperature of 40°C or higher. 3. The method according to item 1, wherein the polymerization is carried out in an inert solvent. 4 The main chain consisting of carbon-carbon bonds has the formula: [In the formula, X represents an acid residue. ] Reactive oxazolinedione ring ()
is characterized by thermally decomposing a polymer having a reactive oxazolinedione ring bound in an amount of 0.1 to 83.3% by weight.An acylisocyanate group is bonded to a main chain consisting of carbon-carbon bonds in an amount of 0.1 to 72.2% by weight. A method for producing an acylisocyanate group-containing polymer having a molecular weight of 1,000 to 100,000. 5. The method according to item 4, wherein the thermal decomposition is carried out at a temperature of 40°C or higher.