JPS61272207A - Blocked acylisocyanate group-containing polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a novel polymer useful as a coating compound, adhesive, etc., by polymerizing a specific blocked isocyanated compound so that a specific amount of a blocked isocyanate group is bonded to a main chain consisting of C-C bond. CONSTITUTION:A blocked isocyanate compound shown by the formula I (R is H or lower alkyl B is residue obtained by removing H participating in addition reaction from blocking agent such as CH3OH, etc.) is polymerized alone or with a monomer (e.g., styrene, etc.) containing no active hydrogen, to give a novel polymer having 1,000-100,000 molecular weight and 0.1-99.9wt% blocked isocyanate group shown by the formula II bonded to a main chain consisting of C-C bond. EFFECT:The introduced blocked acylisocyanate group is easily dissociated by heat, light, catalyst, etc., to form a highly reactive acylisocyanate group, but the polymer is a stable precursor having this group blocked and it is easily handled.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a novel polymer, particularly a main chain consisting of carbon-carbon bonds, having the formula; Residues with hydrogen atoms removed are shown. ] The present invention relates to a blocked acylisonoanate group-containing polymer having a molecular weight of 1000 to 100,000 and having a molecular weight of 1000 to 100,000, in which blocked acylisocyanate groups are bonded in a proportion of O11 to 99.9% by weight, and a method for producing the same.

BACKGROUND OF THE INVENTION Compounds carrying 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 of these functional groups participate in various reactions with different reaction mechanisms. You can. Focusing on such usefulness, the present inventors previously provided an isocyanate compound represented by the following formula [Japanese Patent Application No. 58-2252]
No. 26]: In the formula, R represents a lower alkyl group. Ko. The method of the invention can also be used when R is hydrogen.

Furthermore, the present inventors have prepared the above isocyanate compound (II)
The present invention provides a polymer having a monomer of

The acyl isocyanate group (-C-N=C=O) introduced into these polymers has a carbonyl group adjacent to the isocyanate group, and this carbonyl group increases the activity of the isocyanate group, allowing a wide variety of addition reactions, etc. It is in a state where it can operate. Therefore, acylisocyanate group-containing polymers have a wide range of uses and usefulness.

(Objective of the Invention) As mentioned above, the present invention is directed to blocking the highly reactive acylisocyanate groups with a blocking agent, for example, to prevent reactivity at room temperature, thereby making it easier to handle the polymer. be.

(Structure of the Invention) That is, the present invention provides a main chain consisting of a carbon-carbon bond [in the formula:
B represents a residue obtained by removing the hydrogen atom involved in the addition reaction from the blocking agent. ] Provided are a blocked acylisocyanate group-containing polymer having a molecular weight of 1,000 to +00,000, in which blocked acylisocyanate groups are bound in a proportion of 0.1 to 99.9% by weight, and a method for producing the same.

The first method for obtaining the blocked acylisocyanate group-containing polymer of the present invention is as follows: indicates a residue obtained by excluding the hydrogen atom involved in the addition reaction from the blocking agent.

] It can be obtained by polymerizing the blocked isocyanate compound (I) represented by the following alone or with other ethylenically unsaturated monomers.

The blocked isocyanate compound (In) is obtained by blocking the isocyanate compound (I[) with a blocking agent represented by the formula: B-H(JV).

The isocyanate compound (II) is obtained from the above-mentioned patent application in 1982.
It may be obtained by the method of No.-225226, but D.
Macromolecule Curare Chemie (DieMakromo
leklare Chemie) l 31 (197
0) 247T-257 (NO, 3199). Isocyanate compound (II), which is a raw material, can usually be produced by a reaction between α-alkylacrylamide and oxalyl halide. The reaction is usually carried out at a temperature of 0 to 80°C in the presence of an inert solvent such as a halogenated hydrocarbon.

As mentioned above, since the isocyanate compound (It) has the possibility of carrying out various reactions, when the blocking agent (IV) is made to act on it, the desired isocyanate compound (n) and the blocking agent In addition to and/or instead of the addition reaction during (IV), trimerization, trimerization, multimerization (polymerization), etc. of the isocyanate compound (II) itself, or the formed blocked isocyanate compound (III
), the resulting blocked isocyanate compound (
The amide NH group of II[) and the isocyanate compound (n
Although it was predicted that various side reactions such as the reaction of () would proceed, it was actually confirmed that the above-mentioned desired reaction proceeds preferentially in a temperature range not exceeding at least 100°C. In particular, at relatively low temperatures not exceeding room temperature (0 to 30°C), only the desired reaction proceeds quantitatively, and various predicted side reactions can be virtually completely avoided.

The blocking agent (IV) used in the present invention is a suitable aliphatic,
It may be any of ring group, aromatic, alkyl monoalcohol, phenolic compound, etc. Specifically, aliphatic alcohols having 1 to 10 carbon atoms, such as methyl, ethyl, chloroethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, 3,3.5-1-
Various alcohols such as lyntylhexanol, 2-ethylhexanol, decyl, aromatic alkyl alcohols such as phenylcarbinol, methylphenylcarbinol, ether bond-containing alcohols such as ethylene glycol monoethyl ether, ethylene glycol mono Phenolic compounds such as butyl ether, such as phenol itself, substituted phenols whose substituents do not have an adverse effect on the product, such as cresol, xylenol, nitrophenol, chlorophenol, ethylphenol and L-butylphenol. If necessary, monoalcohols and phenols having high molecular weight and relatively nonvolatile properties may be used as blocking agents in the present invention in small amounts. Specifically, nonylphenol, -
Functional polyethylene and polypropylene oxides such as Cardewax 550 and the like.

In addition to the above, blocking agents include active methylene compounds (e.g. acetylacetone, malonic acid diethyl ester, etc.),
Lactams (e.g., propyrolactam, butyrolactam, valerolactam, caprolactam, etc.), N-hydroxyimides (e.g., N-hydroxyphthalimide,
N-hydroxyglutarimide, N-hydroxysuccinimide, etc.), oximes (methyl ethyl ketoxime, acetone oxime, cyclohexanone oxime, etc.),
imidazoles (e.g. 1,3-imidazole etc.),
Triazoles (eg, 1,2,3-benzotriazole) and amines (eg, dicyclohexylamine, etc.) may also be used. Blocking agent (IV) is often liquid at room temperature and can itself serve as a reaction medium, but whether blocking agent (IV) is liquid or solid, an inert solvent can be used. is normal. There are no particular restrictions on the inert solvent as long as it does not adversely affect the reaction, and various solvents can be used, including aliphatic hydrocarbons such as pentane, hexane, and heptane, aromatic solvents such as benzene, toluene, and xylene. Hydrocarbons, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin, hydrocarbon solvents such as petroleum ether and petroleum benzene, halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform, and 1,2-dichloroethane, and ethyl Ether solvents such as ether, isopropyl ether, anisole, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, acetophenone, and isophorone; esters such as ethyl acetate and butyl acetate;
It may be appropriately selected from acetonitrile, dimethylformamide, dimethylsulfoxide, and the like. These may be used alone or in mixtures.

It is generally preferred to carry out the reaction at a temperature of -20 to 100°C, but it is advantageous to carry out the reaction near room temperature (0 to 30°C). At high temperatures of 100° C. or higher, side reactions may occur, while at too low temperatures the reaction rate decreases, which is disadvantageous. Although the use of a tin-based catalyst may be considered during the reaction, the necessity of using a catalyst is usually not recognized.

(III) may be polymerized alone to obtain a homopolymer, or may be polymerized with other ethylenically unsaturated monomers having no active hydrogen to obtain a copolymer. Monomers having active hydrogen cannot be used because they react with isone anate groups.

Examples of monomers without active hydrogen are: monoolefin and diolefin hydrocarbons, i.e. monomers with only hydrogen and carbon atoms, such as styrene, α
-Methylstyrene, α-ethylstyrene, isobutylene (2-methyl-propane-■), 2-methyl-butene-
1,2-Methyl-pentene-1,2,3-dimethyl-butene-1,2,3-dimethyl-pentene-L 2,4-
Dimethyl-pentene-1,2,3,3-trimethyl-hebutene-1,2,3-dimethyl-hexene-112,4
-dimethyl-hexene-1,2,5-dimethyl-hexene-1,2-methyl-3-ethyl-pentene-1,2,
3,3-)Lymphylpentene-1,2,3,4-trimethyl-pentene-1,2-methyl-octene-1,2
,6-cystylene-hebutene-1,2,6-dimedylene-octene-112゜3-dimethyl-decene-1,2-methyl-nonadecene-11 ethylene, propylene, butylene, amylene, hexylene, butadiene-1,3 , isoprene, etc.; halogenated monoolefins and diolefin hydrocarbons, i.e. monomers having carbon atoms, hydrogen atoms and one or more halogen atoms, such as α-chlorostyrene,
α-bromostyrene, 2°5-dichlorostyrene, 2.
5-dipromostyrene, 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, l,2-dibromoethylene , 1,2-difluoroethylene, 1,2-short ethylene, chloroethylene (vinyl chloride), 1,1-dichloroethylene (vinylidene chloride), bromoethylene, fluoroethylene, iodoethylene, 1゜■-dibromoethylene, 1. 1
-difluoroethylene, 1.1-short ethylene, 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 acetate, vinyl benzoate, vinyl toluate, vinyl-p-chlorobenzoate, vinyl-〇-chlorobenzoate and similar vinyl halobenzoates, vinyl-p-methoxybenzoate, vinyl-p- Ethoxybenzoate, methyl methacrylate, ethyl methacrylate, proyl 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 agellylate, hexyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, octyl methacrylate,
3,5.5-trimethylhexyl acrylate, decyl acrylate and dodecyl acrylate; isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl valerate, isopropenyl caproate, isopropenyl Propenyl acetate, isopropenyl benzoate, isopropenyl-p-chlorobenzoate, isopropenyl-〇-chlorobenzoate,
Isopropenyl-〇-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 iosito, allyl chloride carbonate, allyl nitrate, allyl thiocyanate, allyl formate, allyl acetate, acetate pro pionate, 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 Amino acetate, allyl acetoacetate, allyl thioacetate, methallyl esters corresponding to these allyl esters, β-ethyl allyl alcohol, β
-propyl allyl alcohol, l-buten-4-ol, 2-methyl-buten-4-ol, 2-(2,2-dimethylpropyl)-1-buten-4-ol and l-
Esters derived from alkenyl alcohols such as 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, diallyl maleate and diethyl geltaconate; organic nitriles such as acrylonitrile, methacrylaterile, ethacrylonitrile, 3-octenenitrile, crotonitrile, oleonitrile and the like.

Polymerization is carried out by radical reaction in the presence of the inert solvent. As the polymerization catalyst, a common radical catalyst is preferably used. For example, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tetramethylthiuram disulfide, 2,2°-azobis(4-methoxy-2,4-dimethylvaleronitrile), acetylcyclohexylsulfonyl peroxide, 2. Examples include 2'-azobis(2,4-dimethylvaleronitrile). The amount of catalyst blended is usually O01 to the amount of monomer.
It is 10% by weight.

The polymerization temperature is usually 20 to 200°C, preferably 80 to 1
The temperature is 50°C.

During polymerization, other additives such as polymerization regulators may be added as desired.

Another method for obtaining the polymers of the present invention is the reverse of the above method, in which compound (■) is first polymerized and the polymer is formed and then blocked. The reagents, conditions, etc. used for the reaction are as described above.

[Functions and Effects] The blocked acylisocyanate group introduced by the method of the present invention is easily dissociated by heat, light, a catalyst, etc. to generate a reactive acylisocyanate group. In particular, blocked acylisocyanate groups can be dissociated at lower temperatures than normal isocyanates. Therefore, it is a stable precursor of highly reactive acylisocyanate groups and is easy to handle.

The acyl isocyanet group produced by the dissociation is used as a reaction site for the crosslinking reaction. The bonds generated by crosslinking are usually acylurethane and acylurea bonds, which have strong intermolecular cohesion and become tough.

It also has a high ability to form intermolecular hydrogen bonds, resulting in a polymer with excellent adhesive properties.

Therefore, the polymer of the present invention can be widely used in paints, adhesives, plastics, elastomers, etc.

(Example) The present invention will be explained in more detail with reference to Examples.

Example■! - 10.05 g of 1-methoxy-2-propatol adduct of copolymer methacryloyl isocyanate blocked with methoxy-2-propatul, 9.99 g of methyl methacrylate, 9.96 g of ethyl acrylate, and V-65 (Wako Pure Chemical Industries, Ltd.) as an initiator. 2 commercially available from Kogyo Co., Ltd.
．． 2'-azobis(2,4-dimethylvaleronitrile)
) 400. o was dissolved in 90 g of dichloroethane, and this was added dropwise over 3 hours to 20 g of toluene heated to 100°C. Then shots (V-65 (200mg),
2 g of toluene) was added and aged for 1.5 hours.
A copolymer with NV=17.5 (polymerization rate 83%) and Mn=6500 was obtained.

Example 5 2-Methyl-2-propatol-blocked copolymer 6.70 g of 2-methyl-2-propatol adduct of methacryloyl isocyanate was added to styrene.

Tafrylate 6.66g, Ethyl acrylate 6゜6
4 g and 35 g of dioxane were heated and dissolved at 110°C. 400 mg of V-65 as an initiator therein.

25 g of butyl acetate was added dropwise over 2.5 hours. After that, 1
．． After aging for 5 hours, NV22 (polymerization rate 88%)
Thus, a copolymer with Mn=6800 was obtained.

Example 9 Methyl ethyl ketoxime blocked copolymer methacryloyl isocyanate 4 g (dichloroethane 7 g
．． 5g solution) and 4g methyl methacrylate.

1 g of styrene, 4 g of butyl acrylate, and 390 mg of V=65 as an initiator were mixed and added dropwise over 3 hours to 8 g of toluene heated to 100°C.

After that, a post-shot (V=65 (65 mg), toluene 6 g) was added, and aging was performed for 1.0 hours, and NV=4
3 (polymerization rate 96%) to obtain a copolymer. The obtained polymer was cooled to 10° C., and a solution of 3.2 g of methyl ethyl ketoxime in 22 g of toluene was added dropwise. The completion of the reaction was confirmed by the disappearance of νNCO absorption by IR spectrum, and the desired copolymer was obtained with Mn=6500.

Example 14 4 g of methacryloyl isocyanate (0.7 g solution in dichloroethane), 9 g of styrene and V-6 as an initiator
Butyl acetate 8 mixed with 5390 mg and heated to 110°C
．． 3 g,) toluene was added dropwise into 3 g of a mixed solvent over 2.5 hours. After that, a later shot (V-65 (65mg)
, butyl acetate Ig) was added, and aging was performed for 1 hour to obtain a copolymer with NV=45 (polymerization rate 90%). The obtained copolymer was allowed to cool to 25°C, and 2.6-di-t-
Butyl-p-cresol 15.8g to butyl acetate 28g
g and added dropwise. Furthermore, as a catalyst, ButS
Add n(OCCH3)t 250 m9 and incubate at 60°C for 5
heated for an hour. The completion of the reaction was determined by IR spectroscopy.

. Confirm by the disappearance of the absorption of M
Obtained at n=9900.

Example 18 2.1 g of 1-methoxy-2-propatol adduct of homopolymer methacryloyl isocyanate blocked with 1-methoxy-2-propatur was added to 2.4 g of dichloroethane.
The initiator V-6563m was dissolved therein by heating at 85°C.
g was dissolved in 3.2 g of dichloroethane and added dropwise. After aging for 2.0 hours, NV=22, (polymerization rate 81
A homopolymer with Mn=2100 was obtained.

Example 20 8.9 g of homopolymer methacryloyl isocyanate blocked with methyl ethyl ketone oxime (in 7 g of dichloroethane), 9 g of butyl acetate, initiator V65166
1 mg to 4 g of butyl acetate heated to 110°C.
It dripped over time. After aging for 3 hours, NV
= 26 (polymerization rate 80%), a homopolymer was obtained. The obtained homopolymer was allowed to cool to room temperature and methyl ethyl ketone 4
．． 4 g was dissolved in 8 g of butyl acetate and added dropwise. The disappearance of νNCO was confirmed by IR spectrum, and the target homopolymer was obtained with Mn=1600.

Example! , 5.9.14.18 or 20. The results are shown in Table-1. Table 11 shows the operating method used in each example (examples 1, 5 and 9
Example 14, 18 and 20 of Manufacturing Method A1 were designated as Manufacturing Method B).

In the table, BMAI represents blocked methacryloyl isocyanate, MMA represents methyl methacrylate, EA represents ethyl acrylate +1 St, styrene, and NBA represents n-butyl acrylate.

Claims (1)

[Claims] 1. Formula in the main chain consisting of carbon-carbon bonds: ▲ Numerical formulas, chemical formulas, tables, etc. Indicates the group. ] The blocked acylisocyanate group represented by 0.
Molecular weight 1000-99.9% by weight
100,000 blocked acylisocyanate group-containing polymer. 2. Formulas: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents hydrogen or a lower alkyl group, and B represents a residue obtained by excluding the hydrogen atom involved in the addition reaction from the blocking agent. ] The blocked acyl isocyanate compound represented by is polymerized alone or with other monomers having no active hydrogen, and the main chain consisting of carbon-carbon bonds has 0.1 to 99.9% of blocked acyl isocyanate groups. 9% by weight
A method for producing a blocked acylisocyanate group-containing polymer having a molecular weight of 1,000 to 100,000. 3. The method according to item 2, wherein the polymerization is carried out in an inert solvent. 4. The main chain consisting of carbon-carbon bonds has an acylisocyanate group of 0.1 to 72.
Molecular weight 1000-10000 combined at a ratio of 2% by weight
An acylisocyanate group-containing polymer having the formula: B-H [wherein B represents a residue obtained by removing a hydrogen atom involved in the addition reaction from the blocking agent. ] A molecular weight of 100 in which blocked acylisocyanate groups are bonded to the main chain consisting of carbon-carbon bonds at a ratio of 0.1 to 99.9% by weight by reacting with a blocking agent represented by
A method for producing a blocked acylisocyanate group-containing polymer, the method comprising obtaining a blocked acylisocyanate group-containing polymer having a molecular weight of 0 to 100,000. 5. The method according to item 4, wherein the reaction is carried out in an inert solvent.