GB1590056A - Transparent copolyamides - Google Patents
Transparent copolyamides Download PDFInfo
- Publication number
- GB1590056A GB1590056A GB13490/78A GB1349078A GB1590056A GB 1590056 A GB1590056 A GB 1590056A GB 13490/78 A GB13490/78 A GB 13490/78A GB 1349078 A GB1349078 A GB 1349078A GB 1590056 A GB1590056 A GB 1590056A
- Authority
- GB
- United Kingdom
- Prior art keywords
- mol
- hexamethylene diamine
- norbornane
- bis
- aminomethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 48
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 26
- ABPUBUORTRHHDZ-UHFFFAOYSA-N [4-(aminomethyl)-3-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1CC2(CN)C(CN)CC1C2 ABPUBUORTRHHDZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004952 Polyamide Substances 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- 230000007704 transition Effects 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
Description
(54) TRANSPARENT COPOLYAMIDES
(71) We, BAYER AKTIENGESELLSCHAFT. a body corporate organised under the
Laws of Germany of 509 Leverkusen, Germany do hereby declare the invention, for which we pray that a patent may be granted to us. and the method by which it is to be performed.
to be particularly described in and by the following statement:
This invention relates to copolyamides of isophthalic acid, hexamethylene diamine and a bis-aminomethyl-norbornane or a mixture of isomers thereof.
Polyamides of isophthalic acid and hexamethylene diamine have been disclosed in US
Patents Nos 2,715,620 and 2,742,496. The dimensional stability of these polyamides at elevated temperatures is insufficient for various purposes. To solve this problem, it has been proposed in German Auslegeschrift No. 1.267,846 to prepare copolyamides with terephthalic acid.
Although this method raises the melting point of the products. it does not raise the transition temperature or dimensional stability in heat. But it is the transition temperature which is the essential criterion for assessing the heat resistance of amorphous polymers.
It has surprisingly been found that. by partly replacing hexamethylene diamine by a bis-aminomethyl-norbornane or an isomeric mixture of bis-aminomethyl-norbornanes, it is possible to raise the transition temperature of polyamides of isophthalic acid and hexamethylene diamine without destroying the transparency of the polyamides.
This was not quite unobvious in view of the teaching according to German Offenlegungsschrift No. 2,156,723=British Patent 1395595 in which it is stated that polyamides prepared from dicarboxylic acids and bis-aminomethyl-norbornanes, should consist of at least 20 mol% of the amine component of this diamine in order to get transparent polyamides. Copolyamides of adipic acid, bis-aminomethyl-norbornanes and more than 80 mol % of hexamethylene diamine are in fact cloudy.
All the more surprising is it therefore that this loss of transparency does not occur in the polyamides according to the invention.
The present invention thus relates to transparent copolymers consisting essentially of more than 80 to 99 mol %, preferably 82 to 95 mol %, of units having the structure represented by the following formula:
and 1 to less than 20 mol %, preferably 5 to 18 mol %, of units having the structure represented by the following formula:
in which R represents the group I and/or the group II:
Copolyamides which contain the two groups I and II in approximately equal quantities as in the commercially available isomeric mixture of bis-aminomethyl-norbornane are preffered.
The isophthalic acid may be replaced to an extent of up to 20 mol %, preferably up to 10 mol %, by terephthalic acid without affecting the transition temperature of the copolyamides significantly.
The copolyamides are prepared by the usual processes employed for preparing polyamides from diamines and dicarboxylic acids. For example, the mixture preferably containing equivalent quantities of isophthalic acid and of hexamethylene diamine and the isomeric mixture of bis-aminomethyl-norbornane is first heated to a temperature of from 190 to 230"C and then, after termination of this precondensation, polycondensation is completed at a temperature of from 240 to 300"C.
The precondensation may be carried out with or without the addition of water. It may be carried out at atmospheric pressure or in sealed autoclaves at the vapour pressure of water.
The polycondensation may also be carried out with the salts of the monomers.
The amine mixture is preferably composed of more than 80 to 99 mol%, preferably 82 to 95, of hexamethylene diamine and 1 to less than 20 mol%, preferably 5 to 18, of the isomeric mixture of bis-aminomethyl-norbornane.
Any loss of diamine during polycondensation is compensated by using the necessary excess of hexamethylene diamine.
The molecular weight of the copolyamides can be regulated by the usual chain breakers used for polyamides, for example by monocarboxylic acids or amines, preferably benzoic acid, sebacic acid or an excess of isophthalic acid.
The relative viscosity of the copolyamides according to the invention should be higher than 2, preferably between 2.4 and 3.5, determined on a 1% by weight solution of the polyamide in m-cresol at 250C in an Ubbelohde viscosimeter for the production of moulded articles. The copolyamides are transparent and can easily be worked thermoplastically in the usual shaping apparatus. They may contain auxiliary agents and additives such as lubricants, mould release agents, dyes, glass fibres, fillers or fire retardants. The copolyamides may be used for the manufacture of fibres, foils and transparent moulded articles such as panels and injection moulded products.
Example 1
107.3 g of the salt of isophthalic acid and hexamethylene diamine (95 mol % of hexamethylene diamine, based on the diamine content) 3.08 g of bis-aminomethylnorbornane (Manufacturers:Ruhrchemie AG (5 mol% consisting of about equal amounts of 2,5 and 2,6-isomer) and 3.32 g of isophthalic acid are introduced into a round bottomed flask together with an excess of 0.93 g of hexamethylene diamine to compensate for the loss of diamine occuring during polycondensation. The air is displaced by nitrogen and the monomers are polycondensed with stirring at 220"C for 2 hours and then at 270"C for 3 hours. A transparent polyamide having a relative viscosity of 3.2, determined on a 1% by weight solution of the copolyamide in m-cresol at 25"C in an Ubbelohde viscosimeter, is obtained.
The transition temperature determined by differential thermoanalysis is 134"C (Table 1).
Example 2
Various other transparent copolyamides of isophthalic acid, hexamethylene diamine and the mixture of the isomeric bis-aminomethyl-norbornanes manufactured by Ruhrchemie
AG described in Example 1 are prepared by the method according to Example 1 by varying the molar ratios of the diamine components. The transition temperatures obtained are set forth in Table 1.
Comparison Example 1
A polyamide of isophthalic acid and hexamethylene diamine is prepared by the method described in Example 1 but without the addition of the bis-aminomethyl-norbornane mixture. The transition temperature of the polyamide is 1300C.
TABLE 1
Molar Ratio of Transition temperature
Hexamethylene diamine : Bis-aminomethyl- OC norbornane
100 0 130
95 5 134
90 10 139
85 15 144
80 20 148
Comparison Example 2
94.4 g of the salt of adipic acid and hexamethylene diamine, 6.17 g of the bis-aminomethyl-norbornane mixture of Ruhrchemie AG described in Example 1 and 5.84 g of adipic acid and an excess of 2.3 g of hexamethylene diamine are polycondensed as described in Example 1, first at 2200C for half an hour and then at 280"C for two hours.
The molar ratio of hexamethylene diamine : bis-aminomethyl-norbornane mixture is 90: 10. The copolyamide is cloudy.
Cloudy products are also obtained when hexamethylene diamine and the bisaminomethyl-norbornane mixture are used in a molar ratio of 80 : 20 by the polycondensation with adipic acid.
WHAT WE CLAIM IS:
1. Transparent copolyamides consisting of more than 80 to 99 mol %, of units (A) having the structure represented by the following formula
less than 20 to 1 mol %, of units (B) having the structure represented by the following formula
in which R represents the group I and/or the group II:
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (4)
- **WARNING** start of CLMS field may overlap end of DESC **.the molar ratios of the diamine components. The transition temperatures obtained are set forth in Table 1.Comparison Example 1 A polyamide of isophthalic acid and hexamethylene diamine is prepared by the method described in Example 1 but without the addition of the bis-aminomethyl-norbornane mixture. The transition temperature of the polyamide is 1300C.TABLE 1 Molar Ratio of Transition temperature Hexamethylene diamine : Bis-aminomethyl- OC norbornane100 0 13095 5 13490 10 13985 15 14480 20 148 Comparison Example 2 94.4 g of the salt of adipic acid and hexamethylene diamine, 6.17 g of the bis-aminomethyl-norbornane mixture of Ruhrchemie AG described in Example 1 and 5.84 g of adipic acid and an excess of 2.3 g of hexamethylene diamine are polycondensed as described in Example 1, first at 2200C for half an hour and then at 280"C for two hours.The molar ratio of hexamethylene diamine : bis-aminomethyl-norbornane mixture is 90: 10. The copolyamide is cloudy.Cloudy products are also obtained when hexamethylene diamine and the bisaminomethyl-norbornane mixture are used in a molar ratio of 80 : 20 by the polycondensation with adipic acid.WHAT WE CLAIM IS: 1. Transparent copolyamides consisting of more than 80 to 99 mol %, of units (A) having the structure represented by the following formulaless than 20 to 1 mol %, of units (B) having the structure represented by the following formulain which R represents the group I and/or the group II:
- 2. A modification of a copolyamide as claimed in claim 1, characterized in that up to 20 mol %, of the isophthalic acid is replaced by terephthalic acid.
- 3. Copolyamides as claimed in claim 1 consisting of 82 to 95 mol % of units (A) and 18 to 5 mol % of units (B).
- 4. Copolyamides as claimed in claim 2 characterized in that up to 10 mol % of the isophthalic acid is replaced by terephthalic acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772715413 DE2715413A1 (en) | 1977-04-06 | 1977-04-06 | TRANSPARENT COPOLYAMID |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1590056A true GB1590056A (en) | 1981-05-28 |
Family
ID=6005790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB13490/78A Expired GB1590056A (en) | 1977-04-06 | 1978-04-06 | Transparent copolyamides |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS53125497A (en) |
| DE (1) | DE2715413A1 (en) |
| FR (1) | FR2386574A1 (en) |
| GB (1) | GB1590056A (en) |
| IT (1) | IT7848728A0 (en) |
| NL (1) | NL7803628A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU595373B2 (en) * | 1986-08-20 | 1990-03-29 | Mitsui Petrochemical Industries, Ltd. | Aromatic polyamide |
| CN115605528A (en) * | 2020-07-16 | 2023-01-13 | 三井化学株式会社（Jp） | Crystalline polyamide resin, resin composition, and molded article |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5319337A (en) * | 1991-04-05 | 1994-06-07 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Composite molding of resin-bonded magnet for machine parts and process for producing the same |
| KR20230135675A (en) * | 2021-03-30 | 2023-09-25 | 미쓰이 가가쿠 가부시키가이샤 | Polyamide resin composition and polyamide molded body |
| WO2023136207A1 (en) * | 2022-01-12 | 2023-07-20 | 三井化学株式会社 | Polyamide resin composition and polyamide molded body |
| WO2023136205A1 (en) * | 2022-01-12 | 2023-07-20 | 三井化学株式会社 | Polyamide resin composition and polyamide molded article |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE791468A (en) * | 1971-11-16 | 1973-05-16 | Hoechst Ag | TRANSPARENT POLYAMIDES AND THEIR PREPARATION |
-
1977
- 1977-04-06 DE DE19772715413 patent/DE2715413A1/en not_active Withdrawn
-
1978
- 1978-04-04 IT IT7848728A patent/IT7848728A0/en unknown
- 1978-04-04 JP JP3888878A patent/JPS53125497A/en active Pending
- 1978-04-05 NL NL7803628A patent/NL7803628A/en not_active Application Discontinuation
- 1978-04-06 GB GB13490/78A patent/GB1590056A/en not_active Expired
- 1978-04-06 FR FR7810296A patent/FR2386574A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU595373B2 (en) * | 1986-08-20 | 1990-03-29 | Mitsui Petrochemical Industries, Ltd. | Aromatic polyamide |
| CN115605528A (en) * | 2020-07-16 | 2023-01-13 | 三井化学株式会社（Jp） | Crystalline polyamide resin, resin composition, and molded article |
| CN115605528B (en) * | 2020-07-16 | 2024-02-06 | 三井化学株式会社 | Crystalline polyamide resin, resin composition, and molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2715413A1 (en) | 1978-10-12 |
| NL7803628A (en) | 1978-10-10 |
| IT7848728A0 (en) | 1978-04-04 |
| JPS53125497A (en) | 1978-11-01 |
| FR2386574A1 (en) | 1978-11-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |