JPS649334B2 - - Google Patents

Description

Claim 1 Consists of a block of polyetheramide and a block of a random copolymer of a polyetheramide precursor and an ether-free polyamide precursor, without any ether-free polyamide block segment, and having the following repeating structural formula [ -Y]-w [-X]-z [In the formula, [-X]- is the following structural formula and wherein R ₁ , R ₂ and R ₃ are each selected from the group consisting of H, C ₁ -C ₁₀ alkyl and C ₃ -C ₁₀ isoalkyl, and R ₄ are _C1 to _C10 alkylenes and _C3 to _C10
selected from the group consisting of isoalkylenes, R ₅ is
selected from the group consisting of _C0 - _C10 alkylenes, _C3 - _C10 isoalkylenes and _C6 - _C20 arylenes. In the formula, -[-Y-]- is a divalent group of a random copolymer containing etheramide randomly distributed in the polyamide structure, and the amount of etheramide contained in the polyamide structure is The amount is sufficient to form a copolymer having a lower melting point than the corresponding homopolymer of polyamide. Further, w and z each have a value in the range of 4 to 200. A block copolymer having the following. 2 [-X]- is poly(4,7-dioxadecamethylene adipamide) and [-Y]- is poly(4,6-dioxadecamethylene adipamide) precursor and nylon 6,6 precursor A block copolymer according to claim 1 which is a random copolymer of substances. 3. (a) heating a polyether amide salt to a polymerization temperature to form a polyether amide, and (b) heating a mixture of the polyether amide salt and an ether-free polyamide salt to a polymerization temperature to form a polyether amide precursor. (c) melt compounding a mixture of the polyether amide and a random copolymer of the polyether amide precursor and the ether-free polyamide precursor; , a block of polyetheramide forming a block copolymer of polyetheramide and a random copolymer, and a block of random copolymer of a polyetheramide precursor and an ether-free polyamide precursor. , there is no polyamide block segment without ether, and the following repeating structural formula [-Y]-w [-X]-z [where [-X]- is the following structural formula and wherein R ₁ , R ₂ and R ₃ are each selected from the group consisting of H, C ₁ -C ₁₀ alkyl and C ₃ -C ₁₀ isoalkyl, and R ₄ are _C1 to _C10 alkylenes and _C3 to _C10
selected from the group consisting of isoalkylenes, R ₅ is
selected from the group consisting of _C0 - _C10 alkylenes, _C3 - _C10 isoalkylenes and _C6 - _C20 arylenes. In the formula, [-Y]- is a divalent group of a random copolymer containing etheramide randomly distributed in the polyamide structure, and the amount of etheramide contained in the polyamide structure is determined by the amount of etheramide contained in the polyamide structure. The amount is sufficient to form a copolymer with a lower melting point than the corresponding homopolymer. Also, w and z are each 4~
Has a value range of 200. ] A method for producing a block copolymer having the following. 4 Polyetheramide salt is poly(4,7-dioxadecamethyleneadipamide) salt and the ether-free polyamide salt is the nylon 6,6 salt [H ₃ N—(CH ₂ ) ₆ —NH ₃ ] ⁺⁺ [OOC—(CH ₂ ) ₄ —
COO] ^-- the method according to claim 3. [Industrial Field of Application] The present invention relates to a block copolymer consisting of a polyetheramide block and a polyetheramide/polyamide random copolymer block.
One of the two block components of the block copolymer is a polyetheramide, such as poly(dioxa-alkylamide), poly(dioxa-arylamide) or poly(oxer-amide). The other block component is a random copolymer resulting from the polycondensation of the polyether amide precursor and the ether-free polyamide precursor. Block copolymers have utility as fibers, for example, and the random copolymers are formed in part from polyamide precursors. [Problems to be Solved by the Invention] It is believed that polyamides are difficult to form block copolymers because their transamidation reaction rate at temperatures higher than their melting points is relatively fast. An example is nylon 6,6. Fast transamidation reaction rates can be disadvantageous in two-step processing, first, when forming the block copolymer, and second, when melt spinning the block copolymer into fiber. BACKGROUND OF THE INVENTION U.S. Pat. No. 4,130,602 discloses block copolymers of poly(dioxa-alkylamides) and polyamides. U.S. Patent Application No. 773,740, filed March 2, 1977, discloses block copolymers of poly(dioxa-arylamides) and polyamides. United States Patent No.
No. 4,136,133 discloses block copolymers of poly(oxeramide) and polyamide.
U.S. Pat. No. 4,113,794 discloses copolymers of random poly(dioxamide) and polyamide blocks. U.S. Patent No. 4045511
No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, 2003, discloses a method for melt-compounding melt-spun polyamide particles and salts of ether diamines and dicarboxylic acids. U.S. Patent No. 4044071
No. 5, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, 2003, discloses a method for melt compounding a molten melt-spun polyamide and a salt of an ether diamine and a dicarboxylic acid. In the prior art mentioned above, the polyamide portion of the copolymer is essentially polyamide in that, for example, it does not contain ether linkages or dioxa or oxa linkages. In contrast, the polyamide portion of the present invention is in a random copolymer, and no polyamide block segments are formed, and the block segments contain ether bonds. U.S. Pat. No. 3,509,106 discloses that ethylene bis-
Random copolymerized polycondensate of (3-aminopropyl)ether adipate and hexamethylene diammonium adipate (6,6 salt) in which the molar ratio of the former to the latter is, for example, in the range of 9:1 to 1:9. Manufacture has been disclosed. The role of the ether type additive is to increase the water absorption of the resulting polycondensate compared to nylon 6,6 itself.
However, this prior art does not disclose or suggest the use of random cocondensates to form block copolymers with polyetheramides. SUMMARY OF THE INVENTION The present invention resides in a novel composition that is a block copolymer. The copolymer is a block of polyetheramide, such as poly(dioxa-alkylamide),
or poly(dioxa-aryl acid) or poly(oxer-amide) blocks. The other component is a random copolymer resulting from the polycondensation of the polyether amide precursor and the ether-free polyamide precursor. The addition of relatively small amounts of polyetheramide precursor to the polyamide precursor after polymerization of the two results, for example, in lowering the melting point of the latter without substantially altering its other properties. This addition also facilitates processing so that subsequent processing, such as melt compounding, in appropriate amounts will not adversely affect its properties for the desired end use. The block copolymer of the present invention consists of a polyether amide block and a random copolymer block of (1) a polyether amide precursor and (2) an ether-free polyamide precursor. Block copolymers are typically produced by polymerizing a polyetheramide precursor to form polyetheramides, forming a mixture of the polyetheramide precursor and an ether-free polyamide precursor, and polymerizing the mixture. by melt compounding the polyether amide and the random copolymer to form a block copolymer containing the polyether amide block and the random copolymer block. . Random copolymers have lower melting points than the corresponding homopolymers of ether-free polyamides. The block copolymer of the present invention has the following repeating structural formula. The -X- moiety, one of the components of the present invention, is a polyether amide with repeating monomeric units. This unit is selected from the group having the following structural formula. where R ₁ , R ₂ and R ₃ are each selected from the group consisting of H, C ₁ -C ₁₀ alkyl, and C ₃ -C ₁₀ isoalkyl, and R ₄ is C ₁ -C ₁₀ alkylene and C ₃ -C ₁₀ isoalkylene, and _R5 is selected from the group consisting of _C0 - _C10 alkylene, _C3 - _C10 isoalkylene, and _C6 - _C20 arylene. The manufacture of the above is disclosed in the following U.S. Pat.
and U.S. Patent Application No. 2, filed March 2, 1977.
This is clarified in issue 773740. The information contained therein is incorporated herein by reference. These patents also disclose the preparation of precursors, such as salts, used to make the above polymers. One of the precursor salts that can be used to make special polymers belonging to the general class of polymers represented by (A) has the following structure. The above one is also called [30203] ⁺⁺ [6] ⁼ . The number in brackets, for example 3, is the number of carbon atoms, and 0 is the oxygen atom and its relative position. When the above salt is polymerized, it also becomes N-30203-
Forms a polymer also known as 6. Examples of other polyetheramides for which precursors can be used are poly(4,7-dioxadecamethylene sebacamide), poly(4,9-dioxadecamethylene adipamide), poly(4,8 -dioxa-6,6-dimethylundecamethyleneadipamide), poly(4,7-dioxa-2,9-dimethyldodecamethyleneadipamide), poly(4,7-
dioxadecamethylene-2-methyladipamide),
poly(4-oxaheptamethyleneadipamide),
and poly(4-oxa-2,6-dimethyl monomethylene adipamide). The [-Y]- moiety is a divalent group of a random copolymer containing two different monomer units, one of which is randomly distributed in the repeating structure. One of the two different monomer units is a precursor of an ether-free polyamide, while the other is a precursor of the already defined polyether amide. The relative amounts of the two are such that the amount of polyetheramide precursor is sufficient to lower the melting point of the polyamide of the other polymer unit, but not so great that it does not adversely affect the desired properties of the polyamide. be. Generally, the polyetheramide precursor is present in a lesser amount while the other precursor is present in a greater amount. The preferred amount of ether amide in the [-Y]- portion is about 3% by weight.
and about 17% by weight, with more preferred amounts ranging from about 7% to about 13% by weight. The [-Y]-component of the present invention contains a polyamide precursor as one component. Examples of such precursors are caprolactam (nylon 6), hexamethylene diamine salt of adipic acid (nylon 6,
6) and hexamethylene diamine salt of terephthalic acid (nylon 6,T). Also, nylon 6,10 [poly(hexamethylene sebaamide)], nylon 11 [poly(decamethylene carbonamide)],
MXD-6 [poly(meta-xylene adipamide)],
Ethers such as PACM-9 [bis(para-aminocyclohexyl)-methane azelamide], PACM-10 [bis(para-aminocyclohexyl)methane sebacamide], and PACM-12 [bis(para-aminocyclohexyl)methanedecanoamide] Precursors of polyamides without polyamides can also be used.
Others are known to those skilled in the art. See, eg, Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition, Volume 16, Polyamides. The structure of one of the precursors involved in the present invention, namely a polyamide salt (nylon 6,6), is as follows. [―H ₃ N― (CH ₂ ) ₆ ―NH ₃ ]― ⁺⁺ [―OOC―
(CH ₂ ) ₄ ―COO]― ^-- (D) The above can also be called [6] ⁺⁺ [6] ^-- . To make component [-Y]-, a salt such as (C) is mixed with a salt such as (D) or other polyamide precursor. The resulting mixture is heated to a temperature generally above the melting point of the salt, but not above any decomposition temperature. The mixture is maintained at this temperature at atmospheric pressure or above until some or all polycondensation has occurred. During polycondensation, the mixture is often first subjected to pressure and then to vacuum. The latter helps facilitate water removal. Pressure is often used to avoid the escape of volatile substances, such as any diamines formed, that would adversely affect the resulting material. Actual temperatures, pressures, and compounding times will depend on the specific materials used. [-X]- and [-Y] of the block copolymer
―
The polyetheramides present in the parts can be the same or different materials. After the above preparation, the resulting random copolymer using (C) and (D) as an example may have the following structure. ―CCCCDCCCCCCCDDCDCCCCCCCCC― (E) The above shows that (D) is randomly distributed in a copolymer containing a larger amount of (C).
The relative amount of (D) to (C) is such that the melting point of (E) is lower than the melting point of the homopolymer formed by polycondensing the (C) salt itself. However, the amount of (D) relative to (C) is not so great that when incorporated into the final block copolymer, other properties of the homopolymer from (D) itself are adversely affected. From a commercial standpoint, the amount of (D) in the copolymer (C)-(D) preferably ranges from about 3% to about 17% by weight, with about 7% to about 13% by weight. More preferred. A random copolymer, eg (E), is melt compounded with a polyether amide made from eg a salt (C). Thus, the two polymers, polyether amide and random copolymer, are mixed together in a suitable manner. To melt compound the mixture, the temperature of the mixture is raised to at least a temperature above the melting point of the lower melting point polymer, but not above the decomposition temperature of any polymer and/or product. Melt compounding continues until sufficient transamidation reaction has occurred to form the desired block copolymer. In connection with the example just mentioned, the block copolymer consists of the following structure: [Block of -30203-6] - [Block of nylon 6,6 randomly distributed in -30203-6] - What is the transamidation reaction?

Two molecules of the same or different polyamides both containing [Formula]
This is a known phenomenon in which N and C bonds are broken and reformed by bonding with atoms of another molecule. That is, to illustrate, However, if melt compounding continues for too long, the transamidation reaction described above will occur too much and the block copolymer (eg, molecules 1 and 2) will tend to convert to a random copolymer. In general, the molecular weight (number average or weight average) of the block copolymer should be such that the polymer has the physical properties suitable for the desired end use, such as fibers, articles, and films. be. Molecular weights can vary over a wide range to meet the different requirements of a variety of diverse end uses.
Typical molecular weight ranges for block copolymers are from about 5000 to about 5000, on a number average or weight average basis.
It is 100000. Current commercial polyamides such as nylon 6 and nylon 6,6 both have a price of about 12,000~
It has a number average molecular weight range of 30,000. The block copolymer of the present invention has the following repeating structural formula [-X]-w[-Y]-z, where the draft symbols w and z each have a value in the range of about 4 to about 200. I have it too. The above value refers to the number of repeating units contained in [-X]- before the blocks of [-Y]- are connected. For example, a value of 4 represents a value where some molecules may have fewer than 4 repeating units. Nevertheless, there are enough molecules with w and z values greater than 4 that the mixture as a whole is as if each molecule had w and z values of 4. It has the following characteristics. Due to market demand, preferred low values for w and z are about 6-8, while preferred high values are about 125-175. There is no known method for directly measuring the length of blocks in polymer chains. Although NMR could be used, this attempt was unsuccessful. The average length of the blocks is J.Poly.Sci 14 1403 (1976), I. K. mirror. It can be evaluated based on the knowledge of the amide exchange rate of (lKMiller). This method is easy. The melting point of a polymer is a function of block length and can be correlated to the rate of amide exchange. Although the above discussion focuses on making random copolymers by polycondensation of salts, other methods can also be used to make random copolymers. For example, polyether amide and polyamide (ether-free) can be melt compounded for a sufficient time and at a suitable temperature until a random copolymer is formed. Random copolymers made by either method can also be used to make Applicant's block copolymers. The following examples are given to further illustrate the invention. Example 1,2-bis(β-cyanoethoxyethane) or NC—(CH ₂ ) ₂ —O—(CH ₂ ) ₂ —)—
(CH ₂ ) ₂ —,4,7-dioxadecamethylenediamine, NH ₂ (CH ₂ ) ₃ —O—(CH ₂ ) ₂ —O—
(CH ₂ ) ₃ —NH ₂ and poly(4,7-dioxadecamethyleneadipamide), as described in U.S. Pat.
It can be made according to the procedure described in No. 4130602. N-30203-6 salt is made as follows. 204.4g (1.4mol) of adipic acid in methanol
while 246.4g of 30203 diamine dissolved in 906ml
(1.4 mol) in 906 ml of methanol. Add the adipic acid solution to the diamine solution and stir under nitrogen. The resulting mixture is filtered and the recovered salts are air dried in a hood overnight. Add an amount of water to the recovered and dried salt to make a 60% salt solution. Pass the solution through a bed of charcoal to remove the plastids. Add enough diamine to the decolorized solution to adjust the pH of the solution to 7.45. Remove the water by vacuum and dry the salt under vacuum at 60° C. for 2 hours. The other precursor N-6,6 salt is 30203
It is made using the procedure just described, except that the diamine is replaced with 162.4 g of hexamethylene diamine. The [-Y]-component is created as follows. N-6,
Mix 104.3 g of 6 salt with 11.3 g of N-30203-6 salt. Then 50g of the mixture is placed in a tube, the tube is sealed and heated at 190°C for 2 hours. Then open the tube and heat it to 222℃.
Heat under nitrogen (1 atm) for 30 minutes. The latter is then subsequently heated at 275° C. under vacuum for 2 hours. [-Y]-
Ingredients: 90% by weight of N-6,6, N-30203-6
It has a composition of 10% by weight and exhibits the characteristics of a random copolymer. As an illustration of another method, a mixture of N-30203-6 polymer and nylon 6,6 was melt compounded [-Y]-
I made a sample of the ingredients. Melt compounding consisted of stirring at a temperature above the melting point of both polymers, but additional stirring caused little change in the melting temperature of the copolymer obtained by differential scanning calorimetry (DSC). Until then, I had gotten used to stirring. This is shown in the attached table. Thus, the data show that melt compounding a mixture of polyetheramide N-30203-6 and nylon 6,6 at 283° C. for 360 minutes resulted in a random copolymer. This conclusion was tested by heating a mixture of 30203-6 polyetheramide and nylon 6-6 precursor salts to form a copolymer, which was tested for dissolution in formic acid. It was done. Its solubility was very similar, but not equivalent, to the reported solubility of the copolymer made by melt compounding at 360 minutes, 283㎓. However, additional blending would have made the polymers even as determined by solubility testing. The formic acid solubility test is known to test the degree of randomness.

[Table] The [-X]-component is made as follows. N-
Put 50g of 30203-6 into a tube, seal the tube and heat to 190℃.
Heat for 2 hours. Open the tube and place it under nitrogen at 222 °C.
Heat for 30 minutes, followed by 2 hours under vacuum at 222°C. Next, the block copolymer of the present invention is prepared as follows. 100g of the dried [-Y]-component, that is, a random copolymer made by polycondensation of salts, and 28.6g of the dried [-X]-component were dry-blended and heated at 255℃ to 285℃.
Heating at 0.degree. C. for about 15 minutes to about 2 hours provides the desired amount of transamidation. The resulting block copolymer has a total composition of 70/30% by weight N-6,6/N-30203-6. The resulting block copolymer has a melting point of about 225°C and can be melt spun at about 250°C essentially without further rearrangement. 90% by weight of nylon-6 and 10% of N-30203-6
% by weight random copolymer was prepared, and its melting point was 25°C lower than the melting point of nylon-6 (220°C).
The random copolymer is then melt blended with the N-30203-6 copolymer and the resulting block copolymer has a lower melting point than a similar block copolymer without the ether in the nylon-6 portion. Using the above procedure, convert N-30203-6 to the structural formula (B) on page 4.
(R ₁ , R ₂ , R ₃ and R ₅ are the same as for N-30203-6), the resulting block copolymer is a similar block in which the nylon-6 is present but without the ether. It has a lower melting point than copolymers. Use of other polyamides, polyetheramides and their precursors in the above procedure will result in block copolymers with similarly reduced melting points.