DE3818391A1 - Novel block copolymer - Google Patents

Abstract

The present invention relates to a novel block copolymer, especially a block copolymer whose solution is transparent and highly stable even if no halogen-containing solvents are used and which has improved physical properties, such as lightfastness and hydrolysis resistance, and utilises the advantages of amino acid and is formed from amino acid and linear macromolecular compounds. Block copolymers formed from amino acid and linear macromolecular compounds were considered as one of the materials which have remarkably long-lasting properties as coatings for natural leather and synthetic fibres, the linear macromolecular compounds being characterised by the elasticity thereof, and the polypeptide structure of the polyamino acid portion is similar to that in proteins. However, such block copolymers were only soluble in halogen-containing solvents, such as dichloroethane and trichloroethane, to obtain a transparent and stable solution. Since, however, halogen-containing solvents are harmful, their use is not to be preferred having regard to the safety of the factory environment for the workers who are concerned with the manufacture of synthetic leather, the coating of the surface of textiles and the like with polyamic (polyamino) acid and linear macromolecular compounds. Thus, the present invention was obtained as a result of research work ... Original abstract incomplete.

Description

The present invention relates to a block copolymer, its solution even without halogen-containing solvents is transparent and highly stable and that from polyamino acid and linear high molecular compounds is whose shine, feel (grip) and Heat resistance, which are similar to those of silk what the strengths of polyamino acid are not destroyed and physical properties, such as elasticity and abrasion resistance, the weak points of amino acid are to be improved. This block copolymer is useful as a coating agent on the surface of synthetic leather and synthetic textiles they feel similar to natural fibers.

Made from polyamino acid and linear high-molecular compounds block copolymers made feel remarkable similar to natural leather or animal fibers due to the elasticity through which linear high-molecular compounds, and the polypeptide structure a polyamino acid is similar to that of Proteins and they are one of the materials that are remarkable superior properties as a coating agent on the surface of synthetic leather and synthetic Have fibers.

A method for producing block copolymer formed from polyamino acid and linear high molecular compounds using γ- alkyl glutamic acid as an amino acid component is known in Japanese Examined Patent Publication No. Sho 48-726 and Japanese Examined Patent Publication No. Sho 52 27 681.

However, the block copolymers using γ- alkyl glutamic acid are only soluble in halogen containing solvents such as dichloroethane, trichloroethane and chloroform to form a transparent and stable solution. Although dimethylformamide is also used, the resulting solution is muddy and it is necessary to use halogen-containing solvents as the main solvent component to obtain a transparent and stable solution.

Currently these halogen containing solvents used industrially. The halogen containing solvents are harmful, however, and many facilities for the removal of halogen-containing solvents and the like are required to protect the operating environment for the workers involved in the production of synthetic Leather, coating the surface of textiles or the like are concerned. This was one of the major obstacles with regard to the wide industrial application of these resins.

A method in which amine is added to a mixture comprising urethane prepolymers and γ- alkyl glutamic acid-N-carbonic anhydride to copolymerize urethane with amino acid is disclosed in Japanese Unexamined Patent Application No. Sho 58-57 420, which Japanese Unexamined Patent Application No. Sho 59-1 40 217 or Unexamined Japanese Patent Application No. Sho 61-58 489 has been proposed as a measure to solve problems related to the use of such halogen-containing solvents.

However, although a solution of the polyamino urethane resins obtained by this method is formed, it is difficult to obtain polyamino acid urethane resins which are superior in the transparency and stability of the solution. In addition, since an amino acid component is γ- alkyl glutamic acid, it has been extremely difficult to obtain the polyamino acid urethane resins which are heat-resistant to the extent that heat-embossing of the synthetic leather and heat-setting of the clothes can be carried out easily.

Also, the possibility of using a mixture by adding amino acids such as Glycine and L- or D-alanine, to the amino acid component is obtained in the Japanese Patent Laid-Open Patent described.

Since neutral amino acid polymers γ- alkyl glutamic acid polymers are generally superior in heat resistance, the heat resistance of these resins can be expected to be improved by using the mixture containing glycine and alanine.

However, since the side chains of the amino acid in glycine and Alanine is remarkably short, the hydrophobic Property is reduced and therefore the connectivity of the polyamino acid fraction to organic Solutions decreased remarkably. That's why they're through Mixture of these amino acids obtained in solubility inferior, which makes it very difficult to Get solution of these resins, which in stability is superior to the solution.

Accordingly, the above-mentioned, unexamined Japanese patent applications describe that optically active γ- alkyl glutamic acid is preferably used alone as the amino acid. Therefore, none of the above-described proposals have sufficiently been obtained to date satisfactorily satisfying both physical properties such as heat resistance and stability in non-halogen containing solvents.

In view of this prior art, the inventors, through serious research, have found a block copolymer composed of polyamino acid and linear high molecular compounds, the solution of which is transparent and highly stable even without the use of halogen-containing solvents, and whose physical properties such as light fastness and hydrolysis resistance are improved and which use the strengths of polyamino acid, that the stability in the non-halogen containing solvents is remarkably improved, and also that the light fastness and hydrolysis resistance are improved by using the block copolymer using the linear high molecular compounds with any functional group of the primary amino group, secondary amino group , Epoxy group, isocyanate group and hydroxyl group at one end or both ends thereof and neutral amino acids with large side chains, that is, with an increased hydrophobic property and a great connectivity to organic solvents alone or in combination with ω- alkyl acid amino acid as the amino acid component. As a result, the present invention has been accomplished.

That is, the present invention relates to a block copolymer that of polyamino acid and linear high molecular weight Connections are formed, which by the reaction of amine, neutral amino acid N-carbonic anhydride, which is represented by the general formula below (II)

in the R an alkyl group with 3-7 carbon atoms or

and ω- alkyl acid aminic acid N-carbonic anhydride, which is represented by the following general formula (III)

is shown in which R¹ is an alkyl group with 1-4 Carbon atoms or

n is 1 or 2, obtained on a solution by dissolving linear high molecular compounds (I) such as polyester, polyether and polyurethane which have any functional group of the primary amine, secondary amine, epoxy group, isocyanate group and hydroxyl group on one or both Ends of the molecule were obtained in organic solvents without active oxygen.

According to the present invention, the composition is of compounds (I), (II) and (III) limited as follows:

That is, (I) is used in an amount of 10-90% by weight, based on the total weight of (I), (II) and (III) used and (II) in an amount of 3-100 wt .-%, based on the total weight of (II) and (III) used.

The organic solvents without active hydrogen include amide series solvents such as N, N-dimethylforamide, Formamide, N, N-dimethylacetamide, pyrrolidone and N-methylpyrrolidone, ether series solvents such as dioxane and diethylene glycol dimethyl ether, aromatic Solvents such as benzene, toluene and xylene, solvents the ester series, such as ethyl acetate and butyl acetate,  Ketone series solvents such as methyl ethyl ketone, Methyl isobutyl ketone and cyclohexanone and the like. These solvents can be used in combination will. A solution with a high amino acid content in the copolymer and a high concentration of To obtain copolymers, especially mixtures the solvents of the amide series, solvents of the Ether series and aromatic solvents preferred used.

In addition, according to the present invention, any kind of soluble in the solvents described above linear high molecular compound are used but it is appropriately dependent on the physical Property that is for a particular product are selected. These high molecular weight compounds are listed in Table 1, but they are not always limited to this. You can individually or in combination in any optional ratio be used.  

Table 1

in which R _{1 to 8 is} the following polyether and polyester, n, p and q are positive integers.

In the production of a block copolymer, which from the Polyamino acid and the linear high molecular compounds using this linear high molecular weight Connections is formed, the solution if the Amount of linear high molecular compounds used what is extremely diminished, muddy gelatinized whose stability is reduced. If the set of linear high molecular compounds on the other hand extremely increased the gloss and grip of the polyamino acids remarkably reduced. That is why there is a relationship of the linear high molecular compounds used of 1-90% by weight based on one Total weight including all amino acid N-carbonic anhydrides suitable.

In addition, the influences of a molecular weight of the linear high molecular compounds on physical Properties of the block copolymer obtained which Amino acid and linear high molecular compounds was formed with reference to the properties of the Reaction solution, an elementary analysis of the  fractional block copolymers, an infrared absorption spectrum, the viscosity properties and the like examined with the result that the viscosity the solution with the block copolymer with an increase the molecular weight of the linear high molecular weight Connections has been extremely increased and that if that Molecular weight was too low, the appearance of performance was reduced as a block copolymer, so that Molecular weight of the linear high molecular compounds from about 1000-50,000 is most preferred.

The molecular weight of the block copolymer obtained made of polyamino acid and linear high-molecular compounds is 10,000 or more, but if it's 10,000 to 500,000 is a film that is remarkably superior is preserved in physical properties. The representative examples of the neutral amino acid N-carbonic anhydride according to the present invention N-carbonic anhydride of the amino acids, such as valine, Norvaline, leukine, isoleukine, norleukine, phenylalanine and Methionine.

They can either be in optically active form or in racemic Shape can be used. These amino acid N-carbonic anhydrides can be used in combination.

Moreover, the representative examples of ω -Alkylsäureaminosäure-N-N-carbonic anhydride of carbonic γ -Methylglutaminsäure include γ -Äthylglutaminsäure, γ -Benzylglutaminsäure, β -Methylasparginsäure, β -Ethylasparginsäure, β -Benzylasparginsäure and the like. They can be used either in optically active form or in racemic form.

As for the amino acid composition in the block copolymer formed from polyamino acid and linear high molecular compounds according to the present invention, neutral amino acids can be used individually, but in view of the stability of the solution at low temperatures, it is preferred to add ω- alkyl acid amino acids. In addition, from the viewpoint of heat resistance, it is further preferred to use the ω- alkyl acid amino acid N-carbonic anhydride in an amount of 90% by weight or less based on the total weight of all amino acid N-carbonic anhydrides used.

Amines used as a polymerization catalyst in the present Invention used include amines that represented by the following general formulas (IV-VII) such as trimethylamine, triethylamine, tri-n-butylamine, Triethylene diamine, dimethyl diamine, diethylamine, Ethylenediamine, propylenediamine, isophoronediamine, 1,2-cyclohexanediamine, 1,4-cycloexane diamine, o-phenylene diamine, m-phenylenediamine, p-phenylenediamine, toluene-2,4-diamine and 4,4'-diphenylmethane diamine

in which R₁, R₂ and R₃ represent a hydrogen atom or a Represent alkyl group with 1-12 carbon atoms. R₄ a chain or cyclic alkylene group or one represent aromatic ring. Tertiary amines like Triethylamine, Tri-n-Butylamine and Triethyldiamin with a dissociation constant value of 8-11 are from used this preferred.  

The amount used varies depending on of some kind of functional end groups of linear high molecular compounds, but if they are within of the range from 1/10 to 1/1000 based on the total number of moles of amino acid N-carbonic anhydrides used the product is completely satisfactory.

The temperature of the polymerization reaction is not special limited, but in terms of controlling the Reaction of the operation and the like is 10- 80 ° C, preferably 30-50 ° C. Because a concentration of Resin is too high during the polymerization, the Viscosity of the solution also increases considerably, which the solution becomes unwieldy and that's why 3-40 % By weight. A range of 8-20% by weight leads especially to the solution of a block copolymer consisting of an amino acid and linear high molecular compounds is formed with a viscosity that acts as a coating agent is very handy.

The present invention is described individually below Described in relation to the preferred embodiments.

Example 1

44.4 parts of isophorone diisocyanate and 0.03 part of a 10- % toluene solution of dibutyltin laurate became 200 Share polytetramethylene glycol with an average Molecular weight of 2000 added in one Polymerization vessel with stirring at 60 ° C or less introduced and then heated to 100-110 ° C to complete the reaction Perform for 4 hours. After completing the  331 parts of dimethylformamide were added to the reaction, a urethane polymer (A) with terminal isocyanate groups to obtain.

The about 3 g of the urethane polymer (A) obtained were precisely measured and placed in an Erlenmeyer flask, where the urethane polymer (A) dissolved in 10 ml of tetrahydrofuran has been. In addition, 5 ml of an N / 2 solution of the di-n-butylamine chlorobenzene added and the mixture became 10 Minutes left. Then 80 ml of methanol and 4 Drop of a 1% solution of bromophenol blue methanol added as an indicator and then the mix with titrated with an N / 5 solution of sulfuric acid.

And which do not contain the urethane prepolymer (A) Solution was also titrated in the same way to quantitatively determine a terminal isocyanate group with the result that an isocyanate value of the prepolymer (A) is 0.142 g equivalent.

58.8 g of the 42.4% by weight solution of the urethane prepolymer obtained (A) were added to a solution that by dissolving a certain amount of each amino acid N-carbonic anhydride shown in Table 2 in 125 g of dioxane and 50 g of dimethylformamide added and then the resulting mixture became 30 Stirred for minutes. Then a solution came through Dissolution of 0.74 g of isophoronediamine in 75 g of dimethylformamide was added, and it became 5 Stirred at 30 ° C for hours to conduct the reaction.  So was a solution of the polyamino acid urethane resin (B) (a concentration of solid materials of 14.9% by weight).

In Comparative Examples 1 and 2, the preparation in the same way as in Example 1 with the Exception carried out that L-alanine-N-carbonic anhydride has been used. The solution of the polyamino acid urethane resin obtained was made with regard to stability with the Results shown in Table 2 evaluated.  

Table 2

• 1. In the table above, L-LEU: L-leucine-N-carbonic anhydride L-Ala: L-alanine-N-carbonic anhydride means DL-Met: DL-methionine-N-carbonic anhydride L-MG: q -Methyl-L- Glutamic acid-N-carbonic anhydride L-Phe: L-phenylalanine-N-carbonic anhydride
• 2. Rating the stability of the solution: 0: Superior liquid, transparent and flowable. ×: Gelatinized and not liquid.

As can be seen from Table 2, for polyamic acid urethane resin using L-alanine the reaction solution gelatinized, creating the stable solution of the resin could not be obtained. In contrast, was for polyamino acid urethane resins using L-leucine, DL-methionine and L-phenylalanine get clear and stable solution that does not is gelatinized.

Example 2

Solutions by dissolving the specific amounts of the respective amino acid N-carbonic anhydrides described in Table 3 are shown in blending solvents that the respective solvents shown in Table 3 an amount of 125 g and 66.2 g of dimethylformamide contained, were obtained, 58.8 g of the 42.5% Solution of the urethane polymer (A) obtained in Example 1 added and then the resulting mixture became 30 Minutes stirred. Then a solution came through Dissolution of 0.74 g isophorone in 25 g dimethylformamide received, added and the resulting Mixture was stirred for 5 hours to complete the reaction perform a solution of the polyamino acid urethane resin (C) (a concentration of solid materials of 20% by weight) was obtained.  

In Comparative Example 3, the preparation was carried out in the same manner except that γ- methyl-L-glutamic acid-N-carbonic anhydride was used alone. The obtained solution of the polyamino acid urethane resin solution was applied to release paper and dried with a hot wind at 120 ° C. for 5 minutes, from which a transparent film was produced. The thermal properties were checked by measuring the tensile strength in a thermostat at 100 ° C. The solution stability characteristics of the polyamino acid urethane resin solution were also observed, and the results shown in Table 3 were obtained.

Table 3

• 1. 0: Superior liquid, transparent and flowable
  ∆: gelatinized (<10 ° C)
• 2. The measurement conditions were as follows: Sample:
  Thickness 30 µm Width 10 mm Length 30 mm Device:
  Stretching speed 50 mm / min temperature 100 ° C

As can be seen from Table 3, the amino acid urethane resins using L-leucine, DL-methionine and L-phenylalanine-N-carbonic anhydrides have improved solution stability and thermal properties compared to that of the polyamino acid urethane resin in which only γ - Methyl-L-glutamic acid-N-carbonic anhydride is used.

Example 2

0.34 kg of hexamethylene diisocyanate and 0.5 g of a 10% Toluene solution of dibutyltin laurate was added to 1.0 kg of polytetramethylene glycol with an average molecular weight of 1000 added and placed in a reaction tube with a 3 l capacity with stirring at 60-70 ° C introduced and then heated to 110-120 ° C to the Carry out reaction for 4 hours. After completion 1.34 kg of dimethylformamide were added to the reaction,  a urethane prepolymer (D) with terminal To obtain isocyanate groups (a concentration of Solid materials of 50 wt .-%).

77.5 g piperazine anhydride and 500 g dimethylformamide were placed in another reaction vessel and the Mixture was stirred at 30 ° C to dissolve. Then the urethane prepolymer (D) became the resulting Mixture gradually added dropwise. The addition of the urethane prepolymer (D) became one Time stopped when a lot of the amino group that was quantified based on the 1350 ppm Solid materials was.

The amount of the amino group of the reaction mixture obtained was 1270 ppm based on the solid materials. 2.11 kg of dimethylformamide was added to a dimethylformamide solution of the polyurethane with terminal Amino groups and a resin concentration of 25 % By weight.

80 g of solution (E) and 6 g of a 10% toluene solution of tri-n-butylamine was 335 g of a mixed solvent added the dimethylformamide, dioxane and toluene contained in a ratio of 20, 30 and 50 wt .-% and the resulting mixture was on for 5 minutes 40 ° C stirred.

A previously prepared mixture containing 31 g of γ- methyl-L-glutamic acid-N-carbonic anhydride and 16.5 g of L-leucine-N-carbonic anhydride was added to the resulting mixture solution, and then was added at 30-35 for 3 hours ° C was stirred to carry out the reaction, whereby a solution of the polyamino acid urethane block copolymer (a resin concentration of 12.3% by weight) was obtained.

Examples 4-8

The reaction was carried out using amino acids-N- Carbonic anhydrides with the compositions shown in Table 4 carried out in accordance with Example 3, solutions of polyamino acid urethane block copolymers to obtain.

Example 9

60 g of a dimethylformamide solution of the polyurethane obtained in the same manner as in Example 3 and 5 g of epoxy resin (Epicoat 1004 manufactured by Yuka Shell Epoxy Co., Ltd.) were dissolved in 350 g of mixture solvent containing the dimethylformamide, dioxane and toluene contained a ratio of 20, 30 and 50 wt .-%. The resulting solution was heated to 40 ° C. Then 3 g of a 10% triethylamine toluene solution was added and stirred for 30 minutes. A previously prepared mixture containing 31 g of γ- methyl-L-glutamic acid-N-carbonic anhydride and 16.5 parts of L-leucine-N-carbonic anhydride was added to the resulting mixture solution, and the resulting mixture was stirred at 30 for 3 hours -35 ° C to carry out the reaction to obtain a solution of the polyamino acid-epoxy urethane block copolymer which was transparent and superior in stability, had a resin concentration of 12% by weight and had a viscosity of 1200 mPa · s at 30 ° C.

Comparative Examples 4-6

Solutions of the polyamino acid urethane block copolymers below Use of amino acid-N-carbonic anhydrides with the Compositions shown in Table 4 were based on the obtained in the same way as in Example 3.

The solutions of the block copolymer resins described in Examples 3 -9 and in Comparative Examples 4-6 were obtained, were with respect to stability with those in Table 4 results shown evaluated.  

Table 4

Abbreviations for the compositions of amino acid N-carbonic anhydrides and the marks for stability the solution are the same as in Table 2 of Example 1.

As shown in Table 4, the resin solutions were gelatinized using γ- methyl-L-glutamic acid-N-carbonic anhydride alone and in combination with L-alanine-N-carbonic anhydride, whereby the stable solution could not be obtained.

In contrast, the resin solutions were in use of amino acid-N-carbonic anhydrides, which the Examples 3-9 are shown, transparent and stable without being gelatinized and having a viscosity that was suitable for a coating agent.

Then the solutions obtained in the examples were on a release paper with a thickness of 0.25 mm is applied and for 5 minutes at 80 ° C with a hot wind dried and then at 120 ° C for 10 minutes to make a transparent and excellent film. The mechanical properties of the resulting films are shown in Table 5.

Measurement conditions:
Sample:
Width 10 mm length 100 mm stretching speed 50 mm / min temperature 25 ° C
Film thickness (µm) 28 100% modulus of elasticity (kg / cm <100 strength (kg / cm²) 236 elongation (%) 200

As can be seen from Table 5, the resulting are Urethane copolymer resins with physical properties, which are sufficiently durable as a treatment agent are synthetic leather and fibers.

Example 10

59 g of N, N-dimethylamino-1,3-propanediamine were 500 g of obtained solution of the polyamino acid urethane resins of Example 3 was added and the resulting mixture was added subjected to a reaction to remove methyl ester groups in Convert amide groups at 75 ° C for 2 hours. The Termination of methyl ester group conversion reaction in amide groups was determined by the quantitative Determination of the remaining N, N-dimethylamino-1,3- propandiamins by liquid chromatography quantitative approved.

450 g of water became 500 g of the resulting solution Polyamino acid urethane resins with vigorous stirring gradually added to a water-containing Obtain sludge from a water-in-oil-like emulsion.

The resulting sludge containing water was broken up a release paper applied in an amount of 100 g / m² and then dried in 2 hours. That means 5 minutes first at 60 ° C and then at 120 ° C for 5 minutes a microporous film with a uniform cell structure to obtain. The resulting microporous film  was made in terms of moisture permeability, heat resistance and the like checked. The results are shown in Table 6.

In addition, the above-described water-containing slurry of the water-in-oil type emulsion was applied directly to a nylon taffeta of 133 dtex (120 deniers) in an amount of 100 g / m 2 and then dried in 2 hours, that is, first at 60 ° for 5 minutes C and then left at 120 ° C for 5 minutes, then at room temperature for 24 hours to obtain material for use in clothing. The resulting materials were tested for performance as wind protection materials for use in clothing such as moisture permeability and water pressure resistance with the results shown in Table 6. Example 10 Microporous Film
Moisture permeability (g / m² × 24 h) 8000 (JIS Z - 0208)
Cell melting temperature (° C) 230 heat resistance test (100 ° C × 1 h) not unusual

Treatment of the nylon taffeta
Moisture permeability (g / m² × 24 h) 9000 (JIS Z - 0208)
Adhesion (g / cm) 230 Water pressure resistance (mm H₂O) 800 (JIS L - 1071)
Ironing test (160 ° C) is not uncommon

As described above, the products are according to the present invention that according to the comparative examples,  what the stability of the solution, the light fastness and the hydrolysis resistance concerns superior. Furthermore they also meet the physical properties as coating agents of synthetic leather and fibers.

Since non-halogen containing solvents are used is the solution of the copolymers according to the present Invention also superior to conventional ones.

As described above, it was found that since a new block copolymer made from polyamino acid and linear high molecular weight compounds according to the present invention was formed, no halogen-containing solvents contains and a superior stability of the Solution has facilities for coating the surface of synthetic leather, synthetic Fibers and the like and control devices the operating environment are simplified and the Operating effectiveness can be improved. The synthetic Leather and textiles, the surface of which matches the Solution of this copolymer was coated are those superior to that of conventional polyamino acid urethane resins were made, and what the heat resistance concerns.

Claims (5)

1. New block copolymer formed from polyamino acid and linear high molecular compounds by the reaction of

• a) neutral amino acid N-carbonic anhydride, which is represented by the general formula II below and in which R is an alkyl group with 3-7 carbon atoms or means
• b) ω- alkyl acid amino acid-N-carbonic acid anhydride, represented by the following general formula III in which R₂ is an alkyl group with 1-4 carbon atoms or is, n is 1 or 2, and
• c) linear high molecular compounds (I) which comprise any functional group of the primary amine, secondary amine, epoxy group, isocyanate group and hydroxyl group at one end or both ends of the molecule in organic solvents without comprising active oxygen, in the presence of a Catalyst can be obtained.

2. New block copolymer according to claim 1, characterized in that the linear high molecular weight compounds in an amount of 10-90 wt .-%, based on a total weight of the linear high molecular weight compounds, the neutral amino acid N-carbonic anhydride and the l -alkyl acid amino acid anhydride are. 3. New block copolymer according to claim 1, characterized in that the neutral amino acid-N-carbonic anhydride in an amount of 3-100 wt .-%, based on a total weight of the neutral amino acid-N-carbon anhydride and ω- alkyl acid amino acid-N-carbon anhydride is included. 4. New block copolymer according to claim 1, characterized in that that the linear high molecular weight compounds Are urethane prepolymer. 5. New block copolymer according to claim 1, characterized in that the catalyst is an amine, which is represented by the general formulas IV-VII below in which R₁, R₂ and R₃ is a hydrogen atom or an alkyl group having 1-12 carbon atoms, R₄ is a chain or cyclic alkylene group or an aromatic ring.