JPH0123486B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer that has properties ranging from high hardness to elasticity and is water-soluble or water-dispersible.

Conventionally, polyamides having basic tertiary nitrogen atoms in the main chain or side chains are polymers that have both the properties of cationic polymers and the properties of polyamides, and are used in various molded products, fibers, ion exchange resins ( It is applied to fields such as film) and photosensitive resin.

However, these uses require a wide range of physical properties, from hard and rigid to flexible and rubber-elastic, and such polyamides have hard and rigid properties due to the combination of raw materials dicarboxylic acids, diamines, lactams, and omega-amino acids. Although it has been possible to respond to polymers in the low hardness range, it has not yet been possible to obtain a polymer that satisfies physical properties such as strength and elongation and rebound resilience that are comparable to elastomers such as synthetic rubber in the low hardness range. is the current situation.

Therefore, the present inventors conducted extensive studies regarding the production of polymers having basic nitrogen atoms in the main chain or side chains, with the aim of obtaining a polymer that has low hardness, elasticity, and is water-soluble or water-dispersible. As a result, we have finally completed the present invention.

That is, in the present invention, both ends are substantially primary and/or secondary amino groups, have one or more amide bonds, and have a basic tertiary nitrogen atom in the main chain and/or side chain. with an average molecular weight of 300
~20,000 amide compound and a diisocyanate compound are subjected to a urea reaction, and the main chain and/or
Or add 0.2 meq./basic tertiary nitrogen atom to the side chain.
The reaction product having an average molecular weight of 350 to 30,000 and having an average molecular weight of 350 to 30,000 is converted into a quaternizing agent, ummonium salt, by converting some or all of the basic tertiary nitrogen atoms into a quaternizing agent before, during, or after the urea reaction. This is a method for producing a characteristic polymer.

Both terminals used in the present invention are substantially primary or/and secondary amino groups, have one or more amide bonds, and have a basic tertiary nitrogen atom in the main chain and/or side chain. The amide compound having ω-
These are homopolymers, copolymers, or oligomers synthesized from amino acids, lactams, or derivatives thereof, and mixtures of two or more thereof.
The method of making both terminals of the amide compound into substantially primary or/and secondary amino groups is to change the number of reacted moles of the diamine component having primary or/and secondary amino groups to that of the other dicarbonate. This is possible by using an excess of that of the acid.
In the case of ω-amino acids and lactams, this can be achieved by adding known primary and/or secondary diamines. In this case, the molecular weight of the amide compound can be adjusted by adjusting the excess of diamine.

The average molecular weight of the amide compound is 300~
20,000, preferably 500-15,000, especially 500-6,000.

In the present invention, when obtaining an amide compound having a basic tertiary nitrogen atom in the main chain and/or side chain, a monomer having a basic tertiary nitrogen atom in the molecule may be used as a raw material. . As such monomers, polymerization raw materials described in Japanese Patent Publication No. 54-22229 can be used, for example,
Piperazines such as N,N'-bis(3-aminopropyl)piperazine and N-(2-aminoethyl)piperazine, N-alkyl-ε-caprolactam such as N-methyl-ε-caprolactam, α-
α-N,N-dialkylamino-ε-caprolactam such as N,N-dimethylamino-ε-caprolactam, N-alkyl-ω-aminocaproic acid such as N-methyl-ω-aminocaproic acid, α-
Examples include α-N,N-dialkylamino-ω-aminocaproic acid such as N,N-dimethylamino-ω-aminocaproic acid.

Raw materials for the amide compound used in the present invention include:
In addition to the above-mentioned monomers, aliphatic and/or aromatic dicarboxylic acids, diamines, ω-amino acids, lactams, etc., which are commonly used in polyamide polymerization, may be used in combination. Furthermore, typical examples of amide compounds used in the present invention include nylon 6, nylon 6,6, nylon 6,10, nylon 6/6,
6/6, 10 copolymer, nylon 6/6, 6/6,
In addition to various nylons such as 12 copolymers, polyamides obtained from m-xylylene diamine/adipic acid, polyamides obtained from 1,3-bis(aminomethyl)cyclohexane/adipic acid, 2,
Polyamide obtained from 2,4-trimethylhexamethylene diamine and/or 2,4,4-trimethylhexamethylene diamine/adipic acid, ε-caprolactam/adipic acid/hexamethylene diamine/4,4'-diaminodicyclohexylmethane copolymer Coalesced polyamide, or N,
N'-bis(3-aminopropyl)piperazine/
Polyamide obtained from sebacic acid, ε-caprolactam/N,N'-bis(3-aminopropyl)
Piperazine/adipic acid copolyamide, ε-
Caprolactam/N-(2-aminoethyl)piperazine/adipic acid copolyamide, N,
N'-bis(3-aminopropyl)piperazine/
Adipic acid/sebacic acid copolyamide, α-
Polyamide from N,N-dimethylamino-ε-caprolactam, ε-caprolatam/α-N,N
-Dimethylamino-ε-caprolactam copolyamide, α-N,N-dimethylamino-ε-caprolactam/6,6 copolyamide, ε-caprolactam/α-N,N-dimethylamino-ε
-Caprolactam/6,6 copolyamide, ε
-Caprolactam/α-N,N-dimethylamino-ε-caprolactam/6,6/6,10 copolyamide, polyamide from α-N,N-dimethylamino-ω-aminocaproic acid and copolyamide thereof, α , ω-diaminopolyoxyethylene/polyamide from adipic acid, α,ω-diaminopolyoxypropylene/polyamide from adipic acid, ε-caprolactam/α,ω-diaminopoly(oxyethylene-oxypropylene)/adipic acid copolymerization Polyamide, ε-caprolactam/hexamethylenediamine/adipic acid/5-sodium sulfoinphthalic acid copolymer polyamide, ε-caprolactam/hexamethylenediamine/adipic acid/2,4-diphenoxy
6-[P-(sodium sulfophenylamino)]
Examples include polyamides or oligoamides in which both ends are substantially primary or/and secondary amino groups, such as -S-triazine copolyamide.

It should be noted that primary and/or secondary diamines having no amide bond in the molecule may be used in combination as long as the performance, physical properties, etc. of the polymer are not impaired.

Next, examples of diisocyanate compounds that react with the amide compound in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2, 6-cyclohexane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, dianisidine diisocyanate, 3,3'-ditolylene-4,
4′-diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate,
1,3-cyclohexane dimethyl isocyanate, P-xylylene diisocyanate, 1,5-
naphthalene diisocyanate, transvinylene diisocyanate, 2,6-diisocyanate methyl caproate, diphenyl ether-4,
These include 4'-diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, etc., and prepolymers having substantially isocyanate groups at both ends, which are addition reaction products of these diisocyanate compounds and glycol. These diisocyanate compounds may be used alone or in combination. Examples of the glycol include ethylene glycol, 1,2-
Propanediol, 1,3-propanediol,
Alkylene glycols such as tetramethylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,14-decamethylene glycol, bis-(4-oxyphenyl)methane, 1,1-bis(4 -oxyphenyl)methane, 1,1-bis(4-oxyphenyl)ethane, 1,1-bis(4-oxyphenyl)butane, 1,1-bis(4-oxyphenyl)isobutane, 1,1-bis(4-oxyphenyl) ) Alkylene oxide addition of aromatic glycols such as cyclohexane, 2,2-bis(4-oxydiphenyl)butane, m-xylylene glycol, P-xylylene glycol, and the above bis(4-oxyphenyl)alkanes or cycloalkanes N-methyl-diethanolamine, tertiary nitrogen-containing glycols such as 2,2'-phenyliminodiethanol, sulfur-containing glycols such as 2,2'-thiodiethanol, or polyoxyethylene glycol (preferably molecular weight Polyoxypropylene glycol (preferably polyoxypropylene glycol with a molecular weight of 200 to 4000), polytetramethylene ether glycol (preferably polytetramethylene ether glycol with a molecular weight of 200 to 4000), poly( oxyethylene-oxypropylene) glycol, poly(oxyethylene-oxytetramethylene) glycol, α,ω-1,2-polybutadiene glycol and its hydrogenated products, α,ω-1,4-polybutadiene glycol and its water additives , α,
ε-1,2-polybutadiene/1,4-polybutadiene glycol and its hydrogenated product, or polyester diol, for example, with a molecular weight of 200 to
Polyesters (including oligoesters) in which both ends of 6000 are substantially hydroxyl groups, that is, conventionally known dicarboxylic acids or/and diesters thereof,
Examples include polyester obtained from glycol, oxyacid, etc., and polycaprolactone diol. These glycols may be used alone or in combination.

Conventionally known methods can be used to produce a prepolymer having substantially isocyanate groups at both ends by subjecting the diisocyanate compound and the glycol to an addition reaction. Specifically, examples include a method in which both are mixed and reacted with stirring in a solvent-free state, and a method in which both are dissolved in an inert solvent and reacted. Optimal conditions for reaction temperature, reaction time, etc. should be determined by taking into account the reactivity and thermal stability of both. Also, the reaction ratio of both NCO/OH
(equivalence ratio) is preferably 2.0 or more, preferably 2.05 or more.

Note that even if unreacted diisocyanate remains by adding an excess of the diisocyanate compound, this is not a problem as long as it does not adversely affect the reaction with the amide compound having diamine at substantially both ends in the next step.

Next, in the present invention, the reaction between the amide compound and the diisocyanate compound (including prepolymer) is carried out by gradually adding the diisocyanate compound directly or in the form of a solution to the solution of the amide compound while stirring; A method can be used in which both are mixed in a molten state and reacted. A diisocyanate compound masked by a known method such as a lactam may be used as long as it does not particularly adversely affect both reactions.

Also, the reaction ratio of both is primary and/or secondary.
grade amino group/isocyanate group (equivalence ratio) is 1.0
It is preferably 1.02 or more. In this case, even if excess terminal amino groups remain unreacted, there is no particular problem as long as the performance, physical properties, etc. of the polymer obtained therefrom are not adversely affected. Further, if the primary and/or secondary amino group/isocyanate group (equivalence ratio) is less than 1.0, undesirable reactions such as gelation tend to occur. Since the reactivity of amines and isocyanates is extremely high, the reaction between them is possible even in active solvents such as water, alcohols such as methanol, or mixtures of water and alcohols, and the reaction is completed quickly. Although both reactions should be carried out under optimal conditions suited to the system, they proceed rapidly even at relatively low temperatures, such as room temperature.
The reaction ratio between the amide compound and the diisocyanate compound or prepolymer is 97:3 to 3:
97 (weight ratio), preferably 75:25 to 25:75
It is.

As mentioned above, the polymer obtained by the reaction between an amide compound and a diisocyanate compound has a basic tertiary nitrogen atom of 0.2 meq./cm in its main chain or side chain.
It is necessary to have more than g. If it is less than 0.2 meq./g, it is not preferable because it is difficult to become water-soluble or water-dispersible even if it is converted into an ammonium salt with an acid.

The polymer containing a basic tertiary nitrogen atom obtained in this way reacts with a quaternizing agent to become an ammonium salt-type polymer containing a nitrogen atom of the present invention. The reaction may be carried out at any stage before, during or after the reaction of the diisocyanate compound with the diisocyanate compound. Such a reaction method involves dissolving and mixing an amide compound or polymer having a basic tertiary nitrogen atom and a quaternizing agent in an appropriate solvent, or melting and mixing the two at an appropriate temperature. There are methods of reacting, or adding an amide compound or polymer having a basic tertiary nitrogen atom to the gas phase of the quaternizing agent. As the quaternizing agent, known agents such as protonic acids, metal salts, and alkyl halogen compounds can be used. Examples of protonic acids include hydrochloric acid,
Inorganic acids such as sulfuric acid, formic acid, acetic acid, chloroacetic acid, maleic acid, itaconic acid, phthalic acid, adipic acid,
There are organic acids such as acrylic acid and cinnamic acid.

In the present invention, a polymer is obtained by the reaction of an amide compound and a diisocyanate compound, but since the reactivity of both is extremely high, it is possible to use not only an inert solvent but also a reactive solvent such as methyl alcohol. , high solvent selectivity. In addition, by selecting the molecular weight of each amide compound and diisocyanate compound in the reaction,
Alternatively, by appropriately selecting the reaction ratio of amine and isocyanate, it is possible to obtain polymers ranging from highly hard, slightly elastic, to extremely flexible and highly elastic. Similarly, it is also possible to control the content of basic tertiary nitrogen atoms in the resulting polymer by selecting the content in the amide compound or the molecular weight of the amide compound and prepolymer to adjust the water solubility. It has the following characteristics.

The copolymer elastomer obtained by the method of the present invention can be used in various molded products such as fibers, films, and sheets.
It can be effectively used in various applications such as ion exchange resins (membranes), selectively permeable membranes, photosensitive resins, photocurable paints, photoadhesives, ink binders, and paint binders.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Note that in the examples, parts simply refer to parts by weight.

Example 1 Nylon salt 402 of 200 parts of N,N'-bis(3-aminopropyl)piperazine and 202 parts of sebacic acid
Nylon salt of 50 parts of N,N'-bis(3-aminopropyl)piperazine and 36.5 parts of adipic acid
86.5 parts and 83.3 parts of N,N'-bis(3-aminopropyl)piperazine as a terminal amino grouping agent (also serving as a viscosity stabilizer) were melt-polycondensed in an autoclave to obtain a product with a specific viscosity of 1.26 and a melting point of approximately 145. An almost colorless and opaque amide compound was obtained. The obtained amide compound was alcohol-soluble, had an average molecular weight of about 1500, and had substantially primary amino groups at both ends.

Separately, 500 parts of polypropylene glycol (average molecular weight: 2000) was reacted with 95 parts of hexamethylene diisocyanate to obtain a prepolymer having substantially isocyanate groups at both ends.

Then, the amide compound 100 obtained as above
1 part was dissolved in 500 parts of methanol, and 123 parts of the above prepolymer was gradually added to the amide compound solution at room temperature while stirring. Both reactions were completed in 15 minutes. This solution was cast on a Teflon-coated shear plate, methanol was evaporated, and then dried under reduced pressure to obtain a polymer. The obtained polymer has amide bonds, urethane bonds, and urea bonds in the molecule,
It was pale yellow, transparent, flexible, and had rubber elasticity, with a softening point of about 95°C to 105°C and a specific viscosity of about 2.63, and was substantially insoluble in neutral water. Next, this polymer was dissolved in methanol, an ammonium salt was formed with the basic tertiary nitrogen of the piperazine ring in the main chain of the polymer with hydrochloric acid, methanol was removed, and the mixture was dried. The obtained polymer had rubber elasticity with Shore D hardness of 26 and was substantially soluble in neutral water.

Example 2 500 parts of ε-caprolactam, 270 parts of N-(2-aminoethyl)piperazine, 305 parts of adipic acid, 575 parts of nylon salt, and N-(2 40 parts of (aminoethyl)piperazine are melt-polycondensed in an autoclave to produce a pale yellow, transparent, alcohol-soluble amide with a specific viscosity of 1.40, in which both ends are substantially primary or/and secondary amino groups. A compound (average molecular weight approximately 3050) was obtained.

Separately, polyethylene glycol (average molecular weight
1000) 750 parts and hexamethylene diisocyanate
A prepolymer substantially having isocyanate groups at both ends was obtained by reacting with 300 parts.

Next, 92 parts of the amide compound obtained as described above were dissolved in 200 parts of methanol, and 18 parts of the above prepolymer were gradually poured into the amide compound solution at 50° C. while stirring. Both reactions were completed in about 15 minutes.
The viscosity of the reaction solution was about 180 poise. This pale yellow and transparent solution was cast on a Teflon-coated shear glass, and mezeethanol was removed by evaporation to obtain a polymer. The obtained polymer has amide bonds, urethane bonds, and urea bonds in the molecule, and has a softening point of
It was pale yellow, translucent, flexible and elastic, with a specific viscosity of 2.20 and a specific viscosity of 85-95°, and was substantially insoluble in neutral water.

Next, 55 parts of the polymer obtained above was added to methanol.
4 parts of adipic acid was added to this solution to form an ammonium salt with the basic tertiary nitrogen of the piperazine ring in the main chain of the polymer, methanol was removed, and the mixture was dried. The obtained polymer had rubber elasticity with Shore D hardness of 44 and was substantially soluble in neutral water.

Example 3 Nylon salt 737 of 362 parts of N,N'-bis(3-aminopropyl)piperazine and 365 parts of sebacic acid
163 parts, nylon salt of 94 parts of N,N'-bis(3-aminopropyl)piperazine and 69 parts of adipic acid
and 110 parts of N,N-bis(aminopropyl)piperazine as a terminal amino stabilizer were melt-polycondensed in an autoclave to form a water-insoluble, alcohol-soluble compound with a specific viscosity of 1.33 and an average molecular weight of about 1600, with both ends substantially An amide compound having a primary amino group was obtained. 100 parts of this amide compound was dissolved in 500 parts of methanol, and 136 parts of a prepolymer obtained in the same manner as in Example 1 was reacted with this solution by the method described in Example 1 to remove methanol. The resulting polymer, which has amide bonds, urethane bonds, and urea bonds in its molecules, has a softening point of about 105-115°C and a specific viscosity of about 2.20, is pale yellow, transparent, and elastic, and is virtually resistant to neutral water. It was insoluble in By dissolving this polymer in methanol and adding hydrochloric acid, the basic tertiary nitrogen atom of the polymer and hydrochloric acid formed an ammonium salt. The polymer obtained after drying this solution was Shore D
It had an elastic hardness of 36 and was substantially soluble in neutral water.

Example 4 525 parts of ε-caprolactam, N,N'-bis(3
237 parts of -aminopropyl)piperazine, 173 parts of adipic acid nylon salt, and 65 parts of N,N'-bis(3-aminopropyl)piperazine as a terminal aminating agent were melt-polycondensed in an autoclave.
A pale yellow, transparent, alcohol-soluble amide compound (average molecular weight: 2800) having a specific viscosity of 1.35 and having substantially primary amino groups at both ends was obtained. Further, prepolymer 37 obtained by reacting a 50/50 (wt%) random copolymer of polyethylene glycol and tetramethylene glycol (average molecular weight 1984) with hexamethylene glycol by the method described in Example 1
and 100 parts of this amide compound were reacted in methanol, and methanol was removed. The obtained polymer having amide bonds, urethane bonds, and urea bonds in the molecule has a softening point of 96 to 103°C and a specific viscosity of approximately 2.05.
It was pale transparent and elastic, and was virtually insoluble in neutral water. This polymer was dissolved in methanol and hydrochloric acid was added to form an ammonium salt with the basic tertiary nitrogen atom in the polymer. After drying this solution,
The obtained polymer has an elasticity of Shore D hardness of 46,
It was substantially soluble in neutral water.

Claims (1)

[Claims] 1 Both ends are substantially primary and/or secondary
is a class amino group and has one or more amide bonds,
It is obtained by ureating an amide compound having an average molecular weight of 300 to 20,000 and having a basic tertiary nitrogen atom in the main chain and/or side chain with a diisocyanate compound, and having a basic tertiary nitrogen atom in the main chain and/or side chain. Average molecular weight with tertiary nitrogen atoms of 0.2 meq./g or more
A polymer characterized in that part or all of the basic tertiary nitrogen atoms of the reaction product of 350 to 30,000 are ammonium salted with a quaternizing agent before, during, or after the urea reaction. manufacturing method.