JPH01236238A - Production of polyamide of increased terminal carboxyl group content - Google Patents
Production of polyamide of increased terminal carboxyl group contentInfo
- Publication number
- JPH01236238A JPH01236238A JP6197788A JP6197788A JPH01236238A JP H01236238 A JPH01236238 A JP H01236238A JP 6197788 A JP6197788 A JP 6197788A JP 6197788 A JP6197788 A JP 6197788A JP H01236238 A JPH01236238 A JP H01236238A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- terminal
- group content
- terminal carboxyl
- amount
- 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.)
- Granted
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 61
- 229920002647 polyamide Polymers 0.000 title claims abstract description 61
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000000980 acid dye Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000007423 decrease Effects 0.000 abstract description 9
- 239000000975 dye Substances 0.000 abstract description 6
- IOGGBUVFUGPCLQ-UHFFFAOYSA-N 1-[4-(2-oxoazepane-1-carbonyl)benzoyl]azepan-2-one Chemical compound C=1C=C(C(=O)N2C(CCCCC2)=O)C=CC=1C(=O)N1CCCCCC1=O IOGGBUVFUGPCLQ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000004898 kneading Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 12
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- -1 cyclic anhydride Chemical class 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- AHEGXLOBOVFTHG-UHFFFAOYSA-N 1-[3-(2-oxopyrrolidine-1-carbonyl)benzoyl]pyrrolidin-2-one Chemical compound C=1C=CC(C(=O)N2C(CCC2)=O)=CC=1C(=O)N1CCCC1=O AHEGXLOBOVFTHG-UHFFFAOYSA-N 0.000 description 2
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- PMKTZZPISUBWEM-UHFFFAOYSA-N 1,6-bis(2-oxoazepan-1-yl)hexane-1,6-dione Chemical compound C1CCCCC(=O)N1C(=O)CCCCC(=O)N1CCCCCC1=O PMKTZZPISUBWEM-UHFFFAOYSA-N 0.000 description 1
- GGAVJLYKYINLJT-UHFFFAOYSA-N 1-[4-(2-oxopyrrolidine-1-carbonyl)benzoyl]pyrrolidin-2-one Chemical compound C=1C=C(C(=O)N2C(CCC2)=O)C=CC=1C(=O)N1CCCC1=O GGAVJLYKYINLJT-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〈発明の技術分野〉
本発明は、末端カルボキシル基量の増加したポリアミド
の製造方法に関する。更に詳しくは、本発明は、ポリア
ミドに二官能Ｎ−アシルラクタムを添加し、溶融反応さ
せることにより末端アミノ基量を減少させると同時に末
端カルボキシル基を増加させて酸性染料に染まりにくい
ポリアミドを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a polyamide with an increased amount of terminal carboxyl groups. More specifically, the present invention adds a bifunctional N-acyl lactam to a polyamide and performs a melt reaction to reduce the amount of terminal amino groups and at the same time increase the number of terminal carboxyl groups, thereby producing a polyamide that is resistant to staining with acid dyes. Regarding the method.
〈従来技術〉
ナイロン６、ナイロン６６に代表されるポリアミドはそ
の優れた物理的、化学的性質を有していることがらｍ維
、プラスチックス、フィルム等に現在広く用いられてい
る。この場合、繊維、フィルム用途の中にあって、と争
には酸性染料に染まりにくいという特性が要求されるこ
とがある０例えば、カーペットあるいは衣料用途の一部
の分野に使用されるポリアミド繊維において、酸性染料
に染まり易いものと染まりにくいものを組み合わせ、同
一浴で染色することにより濃淡効果を発現させ、製品の
外観、審美性を高めるという方法がよく用いられる。こ
のような酸性染料に染まりにくい淡染色性ポリアミドを
得る際には、末端カルボキシル基量を多く、且つ末端ア
ミノ基量を少なくする必要かある。つまり、末端アミノ
基量が少くなる程酸性染料には染まりにくくなり、また
、末端アミノ基量が一定の場合、末端カルボキシル基か
多い程、酸性染料には染まりにくくなる。このような、
酸性染料に染まりにくいポリアミドを製造する方法はい
くつか知られている。<Prior Art> Polyamides represented by nylon 6 and nylon 66 have excellent physical and chemical properties and are currently widely used in fibers, plastics, films, and the like. In this case, in fiber and film applications, properties such as resistance to acid dyes may be required. For example, in polyamide fibers used in carpets or some areas of clothing applications, A commonly used method is to combine materials that are easily dyed with acid dyes and materials that are difficult to dye, and dye them in the same bath to create a shading effect and improve the appearance and aesthetics of the product. In order to obtain such a lightly dyeable polyamide that is difficult to dye with acid dyes, it is necessary to increase the amount of terminal carboxyl groups and decrease the amount of terminal amino groups. That is, the smaller the amount of terminal amino groups, the more difficult it is to be dyed by acid dyes, and when the amount of terminal amino groups is constant, the more terminal carboxyl groups, the more difficult it is to be dyed by acid dyes. like this,
Several methods are known for producing polyamides that are resistant to acid dyes.
最も一般的で従来より用いられている方法は、重合当初
あるいは重合途中にモノカルボン酸またはジカルボン酸
等の末端停止剤を添加する方法である。しかし、この方
法では、重合速度が非常に遅くなる為生産性が低く、ま
た、あまり高い重合度のポリマーが得にくいという欠点
がある。The most common and conventionally used method is to add a terminal capping agent such as a monocarboxylic acid or dicarboxylic acid at the beginning or during the polymerization. However, this method has the disadvantage that the polymerization rate is very slow, resulting in low productivity, and that it is difficult to obtain a polymer with a very high degree of polymerization.
池の方法として、ポリアミドの溶融加工時に木端停止剤
としてモノカルボン酸、ジカルボン酸等を添加する方法
があるか、この方法では末端停止剤がポリアミド末端の
みならず、分子鎖中のアミド結合にも反応し、分子量の
低下をきたすという致命的欠点がある。Ike's method involves adding monocarboxylic acid, dicarboxylic acid, etc. as a wood end stopper during melt processing of polyamide.In this method, the end stopper is applied not only to the ends of the polyamide but also to the amide bonds in the molecular chain. It has the fatal disadvantage of also reacting with other molecules, resulting in a decrease in molecular weight.
これらの不利益を解決する為、例えば特公昭４４−５４
４号公報では、環状無水物を使用し、下記の如く末端ア
ミノ基とのみ反応させる方法が提案されている。In order to solve these disadvantages, for example,
Publication No. 4 proposes a method using a cyclic anhydride and reacting only with the terminal amino group as described below.
しかるに、この反応は上記アミド形成に止まらず、一部
は次のイミド反応まで進行して水が生成し、この水がポ
リアミドの解重合反応を引き起こすと同時にポリマーの
黄変をも惹起するという問題がある。However, this reaction does not stop at the formation of the above-mentioned amide, but a portion of it progresses to the next imide reaction, producing water, which causes the problem of causing a depolymerization reaction of the polyamide and at the same time causing yellowing of the polymer. There is.
〈発明の目的〉
本発明の目的は、かかる従来の欠点を解消し、分子量の
低下黄変の懸念なく、極めて短時間で末端アミノ基量を
減少させると同時に末端カルボキシル基量を増加させ、
酸性染料に染まりにくいポリアミドを製造する方法を提
供することにある。<Objective of the Invention> The object of the present invention is to eliminate such conventional drawbacks, reduce the amount of terminal amino groups in an extremely short time without worrying about yellowing, and at the same time increase the amount of terminal carboxyl groups.
An object of the present invention is to provide a method for producing polyamide that is resistant to acid dyes.
〈発明の構成〉
本発明者らは、上記の目的を達成せんとして鋭意検討し
た結果、従来鎖伸長剤として知られている二官能Ｎ−ア
シルラクタム化合物を、末端基濃度および水分率が特定
の範囲に規制されたポリアミドと溶融混練するとき、末
端アミノ基量が極減し、他方末端カルボキシル基量は一
挙に増加し、しかも分子量低下が実質的に抑えられたポ
リアミドが得られることを見い出し、本発明に到達した
しのである。<Structure of the Invention> As a result of intensive studies to achieve the above object, the present inventors have developed a bifunctional N-acyllactam compound, conventionally known as a chain extender, with a specific terminal group concentration and moisture content. We have discovered that when melt-kneaded with a polyamide regulated within a range, a polyamide can be obtained in which the amount of terminal amino groups is extremely reduced, while the amount of terminal carboxyl groups is increased all at once, and the decrease in molecular weight is substantially suppressed. We have arrived at the present invention.
かくして、本発明によれば、
下記（ＩＩＩ）および（ＩＩ）式を同時に満足するポリ
アミドに、二官能Ｎ−アシルラクタムを添加して溶融反
応させることにより、下記（Ｉ［［）式を満足するポリ
アミドに変性することを特徴とする末端カルボキシル基
量の増加したポリアミドの製造方法か提供される。Thus, according to the present invention, by adding a bifunctional N-acyl lactam to a polyamide that simultaneously satisfies the following formulas (III) and (II) and causing a melt reaction, a polyamide that satisfies the following formula (I[[)] is obtained. Provided is a method for producing a polyamide with an increased amount of terminal carboxyl groups, which is characterized by modifying the polyamide into a polyamide.
一２０≦ＣＮＨ２−ＣｃｏｏＨ≦２０ （
ｉ ’０．０５≦ポリアミドの水分率（ｔａＸ）≦０．
４ （Ｉ［）ＣＣＯＯＨ−ＣＮＨ２≧３０
（ＩＩＩ ）（ここで、” ＣＣ０ＯＨは
各々ダラム・当量／Ｈ２
１０６グラム単位とする末端アミノ基量、末端カルボキ
シル基量を表わす）
本発明で用いるポリアミドとしては、上記の（Ｔ）およ
び（ＩＩ）の条件を満足するものならいかなるものでも
よいが、その中でもナイロン６゜ナイロン６６、ナイロ
ン４６．ナイロン６・１ｏ、ナイロン１２等の脂肪族ポ
リアミドは特に好ましく用いられる。-20≦CNH2−CcooH≦20 (
i '0.05≦Moisture content of polyamide (taX)≦0.
4 (I[)CCOOH-CNH2≧30
(III) (Here, "CCOOH represents the amount of terminal amino groups and the amount of terminal carboxyl groups, respectively, in units of Durham equivalent/106 grams of H2.) The polyamides used in the present invention include the above (T) and (II). Any material may be used as long as it satisfies the above conditions, but among them, aliphatic polyamides such as nylon 6°, nylon 66, nylon 46, nylon 6.1o, and nylon 12 are particularly preferably used.
また、溶融成形可能な範囲にて、これらポリアミドに、
第三成分例えばテレフタル酸、イソフタル酸等の芳香族
成分を共重合したものであってもよい、勿論このような
ポリアミド中には、予め各種添加剤、例えば紫外線吸収
剤、熱安定剤、Ｂ燃剤、増白剤、滑剤、核剤１Ｍ型剤、
顔料、フィラー等か添加されていてもよく、あるいはポ
リアミドと二官能Ｎ−アシルラクタムの反応の際、これ
ら剤を添加してもよい。In addition, within the range that can be melt-molded, these polyamides,
A third component, such as a copolymerized aromatic component such as terephthalic acid or isophthalic acid, may also be used.Of course, various additives such as ultraviolet absorbers, heat stabilizers, and B reagents may be added to such polyamides in advance. , brightener, lubricant, nucleating agent 1M type agent,
Pigments, fillers, etc. may be added, or these agents may be added during the reaction of the polyamide and the difunctional N-acyl lactam.
次に、本発明の目的を達成するのに重要なポリアミドの
要件、（ＩＩＩ）および（ＩＩ）につ髪＼て述べる。Next, the requirements for polyamides (III) and (II) that are important for achieving the object of the present invention will be described.
第１に、末端基量に関して、末端アミノ基量より末端カ
ルボキシル基量を減じた値（ＮＨ２Ｃ）が２０以下であ
ることが必要である（ＩのＯＯＨ
要件）、この差が２０を越えるポリアミドでは二宮ａＮ
−アシルラクタムと反応させても、末端アミノ基は減少
するものの末端カルボキシル基の増加は殆ど期待できな
い、そして、本発明はこの末端基量の差が±１５、更に
好ましくは±１０のポリアミドつまり、末端調節剤を用
いることなく、水の存在下通常の重合を行なって得られ
たポリアミドに対して特に有用である。First, regarding the amount of terminal groups, the value obtained by subtracting the amount of terminal carboxyl groups from the amount of terminal amino groups (NH2C) must be 20 or less (OOH requirement of I), and in polyamides where this difference exceeds 20, Ninomiya aN
Even when reacted with an acyllactam, although the terminal amino groups decrease, it is hardly expected that the terminal carboxyl groups increase.The present invention uses polyamides with a difference in the amount of terminal groups of ±15, more preferably ±10, that is, It is particularly useful for polyamides obtained by conventional polymerization in the presence of water without the use of terminal regulators.
第２に、ポリアミドの水分率（Ｗ）が０．０５〜０．４
％の範囲になければならない、このＷの値が０．０５未
満では、例えば上記（ＩＩＩ）の要件は満足しても、上
記アシルラクタムによる末端アミノ基減少、末端カルボ
キシル基増加という特異な現象は起り得ない、他方、該
Ｗが０．４％を越えると、解重合等ポリマー品質に問題
が生じる。Second, the moisture content (W) of polyamide is 0.05 to 0.4.
If the value of W is less than 0.05, for example, even if the above requirement (III) is satisfied, the peculiar phenomenon of decreasing terminal amino groups and increasing terminal carboxyl groups due to the acyllactam will not occur. On the other hand, if the W exceeds 0.4%, problems with polymer quality such as depolymerization will occur.
所で、本発明で用いる二官能Ｎ−アシルラクタム化合物
とは、次の一般式で表されるものである。By the way, the bifunctional N-acyl lactam compound used in the present invention is represented by the following general formula.
（ここに、Ｘはアルキル基あるいは芳香族基を、Ｒはア
ルキル基を表す）
かかる−数式で表される化合物の具体例とじては、Ｎ、
Ｎ’−テレフタロイルビス−ε−カプロラクタム、Ｎ、
Ｎ′−イソフタロイルビス−ε−カグロラクタム、Ｎ、
Ｎ’−アジポイルビス−ε−カプロラクタム、Ｎ、Ｎ’
−アジポイルビス−ε−バレロラクタム、Ｎ、Ｎ′−イ
ソフタロイルビスバレ口ラうタム、Ｎ、Ｎ’−イソフタ
ロイルビスブチロラクタム、Ｎ、Ｎ′−テレフタロイル
ビスブチロラクタム等を挙げることが出来る。これら化
合物は相当するカルボン酸シバライドとラクタムをアミ
ノあるいはＫＯＨ等無機アルカリの存在下に反応させる
ことにより容易に合成することができる。(Here, X represents an alkyl group or an aromatic group, and R represents an alkyl group.) Specific examples of compounds represented by this formula include N,
N'-terephthaloyl bis-ε-caprolactam, N,
N'-Isophthaloylbis-ε-caglolactam, N,
N'-adipoyl bis-ε-caprolactam, N, N'
-Adipoylbis-ε-valerolactam, N,N'-isophthaloylbisbutyrolactam, N,N'-isophthaloylbisbutyrolactam, N,N'-terephthaloylbisbutyrolactam, etc. I can list them. These compounds can be easily synthesized by reacting the corresponding carboxylic acid cybaride and lactam in the presence of an inorganic alkali such as amino or KOH.
本発明において、前記（ＩＩＩ）および（Ｉｔ）式を同
時に満足するポリアミドと二官能Ｎ−アシルラクタム化
合物を反応させるには、ポリアミドの重合終期に重合釜
の中に前記ラクタムを添加撹拌させてもよく、また繊維
、フィルム等の成形加工時、エクストルーダー中で両者
を溶融混練する手段を採用することができる。特に、後
者の方法の場合、ポリアミドチップに該アシルラクタム
をトライブレンドして、これを混練溶融する方法、ある
いはこのアシルラクタムをε−カプロラクタム等に溶解
して、エクストルーダー人口から計量注入する方法等が
ある。In the present invention, in order to react the polyamide that satisfies the above formulas (III) and (It) at the same time with the bifunctional N-acyl lactam compound, the lactam may be added and stirred into the polymerization pot at the final stage of polymerization of the polyamide. Furthermore, when forming fibers, films, etc., it is possible to adopt a method of melting and kneading both in an extruder. In particular, in the case of the latter method, the acyl lactam is triblended with polyamide chips and kneaded and melted, or the acyl lactam is dissolved in ε-caprolactam etc. and metered and injected from the extruder. There is.
ここで、ポリアミドに対する二官能Ｎ−アミノラクタム
の添加量は、目的とする末端基ｌによって変ってくるが
、一般にはポリマーの末端アミノ基と当量〜２倍当量程
度にするのが好ましい、この量が少なすぎると末端カル
ボキシル基と末端アミノ基の差が小さくなって、酸性染
料に対する親和性が増大するので好ましくない、又、余
り多く用いると、分子量低下が大きくなり、しかも成形
体中のラクタムモノマー量が多くなる。Here, the amount of difunctional N-aminolactam added to the polyamide varies depending on the desired terminal group l, but in general, it is preferable to add from equivalent to twice the amount of the terminal amino group of the polymer. If too little is used, the difference between the terminal carboxyl group and the terminal amino group becomes small, which increases the affinity for acidic dyes, which is undesirable.If too much is used, the molecular weight decreases greatly, and the lactam monomer in the molded product is The amount increases.
この溶融混練時の反応温度は、用いるポリアミドの融点
より１０〜１５０℃高い範囲、好ましくは、２０〜８０
℃の範囲にあればよく、また反応時間は、反応温度、ポ
リマー水分によって異なるが、１〜２０分、好ましくは
、２〜６分である。The reaction temperature during this melt-kneading ranges from 10 to 150°C higher than the melting point of the polyamide used, preferably from 20 to 80°C.
℃ range, and the reaction time varies depending on the reaction temperature and polymer moisture content, but is 1 to 20 minutes, preferably 2 to 6 minutes.
〈発明の作用・効果〉
本発明は、ポリアミドに２官能Ｎ−アシルラクタムを添
加反応させるに当り、ポリマーとして末端アミノ基とカ
ルボキシル基の差ＣＮｉ＋２−ＣＣ０ＯＨが２０グラム
当、！／１０”ダラム以下であるポリアミドを用いると
き、アミノ基の極減、カルボキシル基の増加という併合
的現象が起る、という全く新しい知見に基づくものであ
る。<Operations and Effects of the Invention> In the present invention, when adding and reacting a bifunctional N-acyl lactam to a polyamide, the difference between the terminal amino group and the carboxyl group as a polymer, CNi+2-CC0OH, is obtained per 20 grams! This is based on the completely new finding that when using a polyamide with a durum of less than /10", a combined phenomenon of a significant decrease in amino groups and an increase in carboxyl groups occurs.
二官能Ｎ−アシルラクタム自体、ポリアミドの末端アミ
ノ基との反応性が非常に高く、アミノ基と反応すること
によりアミド結合を生成するが、反応するアミノ末端が
消費された場合、ポリマー中の水分により加水分解を受
け、カルボ壽シル基が生成する。従って、Ｃ−ＣＣｏｏ
ｌが２０グラムＮｌ＋□
当量／１０６グラムより多いポリアミドを用いた場合、
目的の酸性染料に染まりにくいポリマーを得る為には多
量のＮ−アシルラクタムを添加する必要性が生じ、経済
的にも好ましくないばかりでなく、成形体中のラクタム
モノマー量が多くなり品質的に好ましくないものしか得
られない。The bifunctional N-acyl lactam itself has very high reactivity with the terminal amino groups of polyamide, and generates amide bonds by reacting with the amino groups, but when the reactive amino terminals are consumed, water in the polymer increases. It undergoes hydrolysis and a carboxyl group is generated. Therefore, C-CCoo
When l is more than 20 grams Nl + □ equivalent/106 grams of polyamide,
In order to obtain the desired polymer that does not easily stain with acid dyes, it becomes necessary to add a large amount of N-acyl lactam, which is not only economically undesirable, but also increases the amount of lactam monomer in the molded product, resulting in poor quality. You only get what you don't like.
このようにして、本発明により、通常のポリアミドから
カルボキシル末端基の多い酸性染料に染まりにくいポリ
アミドを容易に得ることが可能となる。In this way, according to the present invention, it is possible to easily obtain a polyamide having a large number of carboxyl terminal groups and being resistant to dyeing with acid dyes from a normal polyamide.
尚、特公昭５７−５３１６９号公報には、ポリアミドの
分子量を向上させるため、Ｎ−アシルラクタムをポリア
ミドと溶融混練することが示されている。Incidentally, Japanese Patent Publication No. 57-53169 discloses that an N-acyllactam is melt-kneaded with a polyamide in order to improve the molecular weight of the polyamide.
しかし、この方法はあくまで、該アシルラクタムによる
ポリアミドの新伸長を目的とするもので、本発明の如く
、アミノ末端基を極減させ他方、カルボキシル基量を著
しく増大させるような認識はない、このことは同公報の
実施例を参照しても、ベースポリマーのＣＮ１ｌ□−Ｃ
ＣＯＯＨが２０をはるかに越えていることからも矧知で
きる。However, this method is only aimed at new elongation of polyamide using the acyllactam, and there is no recognition that this method minimizes the number of amino terminal groups while significantly increasing the amount of carboxyl groups, as in the present invention. This is true even when referring to the examples in the same publication, the base polymer CN1l□-C
This can be confirmed from the fact that COOH is far over 20.
〈実施例〉
以下、実施例を挙げて説明するが、本発明はこれに限定
されるものではない。<Example> The present invention will be described below with reference to Examples, but the present invention is not limited thereto.
試験・測定法の定義
ａ、固有粘度〈［η］
ポリマー０．２ ｇ、 ０．４ ｔ、 ０．８ ｇを夫
々１００［ｎｌのメタクレゾールに溶解し、３５°Ｃに
てη ｒｅｌ（ｔ／ｌｏ）を測定する６次に、各濃度Ｃ
（ｒ／１００ｍ１）に対しηｒｅｌ−１／Ｃをプｏ ッ
トし、３点から得られる直線の切片から［η］を求めた
。Definition of test and measurement method a, Intrinsic viscosity <[η] 0.2 g, 0.4 t, and 0.8 g of polymer were dissolved in 100 [nl of metacresol, respectively, and η rel (t /lo) 6 Next, each concentration C
(r/100m1) was plotted with ηrel-1/C, and [η] was determined from the intercept of the straight line obtained from the three points.
尚、硫酸中で求めたηｒｅｌと上記の固有粘度［η］と
の関係は［７７］ ＝０．５６７７ ｒｅｌ−０，２６
で表され、例えは特開昭６１−１７１７３２号公報実施
例２のηｒｅ！＝３．６２は固有粘度［η］＝１．７７
に相当する。The relationship between ηrel determined in sulfuric acid and the above intrinsic viscosity [η] is [77] = 0.5677 rel-0,26
For example, ηre! in Example 2 of Japanese Patent Application Laid-Open No. 171732/1982. = 3.62 is intrinsic viscosity [η] = 1.77
corresponds to
ｂ、末端基量
末端基量ＣＮＨ２はポリマーをｍ−クレゾールに溶解し
、０．０１Ｎ ｐ −トルエンスルホジ酸で滴定して求
めた。ＣＣＱＯｔｌはポリマーをベンジルアルコールに
溶解し、・０．１Ｎ水酸化ナトリウムで滴定して求めた
。b. Terminal group amount The terminal group amount CNH2 was determined by dissolving the polymer in m-cresol and titrating with 0.01N p-toluenesulfodiic acid. CCQOtl was determined by dissolving the polymer in benzyl alcohol and titrating with 0.1N sodium hydroxide.
実施例１〜４および比教例１〜４
ε−シカ１０ラクタム水を用いて溶融重合し、熱水洗浄
乾燥することにより水分を調整して得た、モノマー含率
０．５〜１．０％、末端アミノ基４度４４゜末端カルボ
キシル基濃度４７．［η］ １．３４のナイロン６チッ
プに、Ｎ、Ｎ′−テレフタロイルビスカプロラクタム粉
体を下記表−１に示す所定量でトライブレンドし、窒素
気流下、反応温度２５０℃。Examples 1 to 4 and Examples 1 to 4 Monomer content 0.5 to 1.0 obtained by melt polymerizing using ε-Cica 10 lactam water and adjusting the water content by washing and drying with hot water. %, terminal amino group 4 degrees 44° terminal carboxyl group concentration 47. [η] N,N'-terephthaloyl biscaprolactam powder was triblended to 1.34 nylon 6 chips in a predetermined amount shown in Table 1 below, and the reaction temperature was 250°C under a nitrogen stream.
滞留時間４分で溶融混線反応させたところ、表−１に示
す物性のポリアミドが得られた。この時得られたポリア
ミドは着色もゲル化もしていなかった。When the melt crosstalk reaction was carried out at a residence time of 4 minutes, a polyamide having the physical properties shown in Table 1 was obtained. The polyamide obtained at this time was neither colored nor gelled.
又、比較のため、何等の添加剤も加えないで同じ操作を
行った場合及び、ＣＮＨ２’ Ｃ０ＯＨが２０グラム当
量／１０６グラムより多いベースポリマーを用いた場合
について、その結果を表−１に併記した。For comparison, the results are also shown in Table 1 when the same operation was performed without adding any additives and when a base polymer containing more than 20 g equivalent/106 g of CNH2'C0OH was used. did.
実施例５〜７および比較例５
ε−カプロラクタムを水を用いて溶融重合して得た、未
反応モノマー含率的１０％、末端アミノ基潰度４５．末
端カルボキシル基濃度４８．［η］ １．２４のナイロ
ン６チップに、Ｎ、Ｎ′−テレフタロイルビスカプロラ
クタム粉体を下記衣−２に示す所定量でトライブレンド
し、窒素気流下、反応温度２５０”Ｃ，滞留時間４分で
溶融混線反応させた。得られたポリアミドを４時間熱水
洗浄後、１６時間真空乾燥させ、ポリマー特性を測定し
たところ、表−２に示す通りであった。Examples 5 to 7 and Comparative Example 5 ε-caprolactam was melt-polymerized using water, unreacted monomer content 10%, terminal amino group crushing degree 45. Terminal carboxyl group concentration 48. [η] Tri-blend N,N'-terephthaloyl biscaprolactam powder in the specified amount shown in Clothing-2 below to 1.24 nylon 6 chips, under nitrogen flow, reaction temperature 250"C, residence time. A melt-mixing reaction was carried out for 4 minutes.The obtained polyamide was washed with hot water for 4 hours and then dried in vacuum for 16 hours, and the polymer properties were measured as shown in Table 2.
この時得られたポリアミドは着色もゲル化もしておらず
、未反応モノマーを含有していても、反応性に問題はな
かった。又、比較のため、何等の添加剤も加えないで同
じ操作を行った場合についても、その結果を表−２に併
記した。The polyamide obtained at this time was neither colored nor gelled, and even though it contained unreacted monomers, there was no problem in reactivity. For comparison, the results of the same operation performed without adding any additives are also shown in Table 2.
実施例７および比較例３
ε−カプロラクタムを水を用いて溶融重合し、次いで熱
水洗浄、乾燥して得た、水分率０．１５％。Example 7 and Comparative Example 3 ε-caprolactam was melt-polymerized using water, then washed with hot water, and dried, with a moisture content of 0.15%.
モノマー含率０．５〜１．０％、末端基濃度４６．末端
カルボキシル基漂度４８．［η］ １．３４のナイロン
６チップに、Ｎ、Ｎ′−テレフタロイルビスカプロラク
タム粉体を１．２５ｗｔ％トライブレンドし、窒素気流
下、６５市溶融混練押出機にて、反応温度２５０°Ｃ１
滞留時間４分で溶融混練反応させながら、直径０．ｆ３
ｏ＋ｍ、 ６８ホールの紡糸口金を用いて、溶融紡糸、
延伸を行った。溶融反応後のポリアミド特性を表−３（
２）に、延伸糸の糸物性を表−３（３Ｉに示す。Monomer content 0.5-1.0%, end group concentration 46. Terminal carboxyl group drift degree 48. [η] 1.34 nylon 6 chips were triblended with 1.25 wt% of N,N'-terephthaloyl biscaprolactam powder, and the reaction temperature was 250° in a 65-city melt-kneading extruder under a nitrogen stream. C1
While performing the melt-kneading reaction with a residence time of 4 minutes, the diameter of 0. f3
o+m, melt spinning using a 68-hole spinneret,
Stretching was performed. Table 3 shows the properties of polyamide after melt reaction (
2), the yarn physical properties of the drawn yarn are shown in Table 3 (3I).
又、比較の為、水分率を０．１０％に調整し、何等の添
加剤も加えないで同じ操作を行い、得らたれポリアミド
の特性、及び延伸糸の糸物性を比較例として表−３に併
記した。For comparison, the moisture content was adjusted to 0.10% and the same operation was performed without adding any additives, and the properties of the resulting polyamide and the yarn physical properties of the drawn yarn are shown in Table 3 as a comparative example. Also listed.
次いで３６ゲ一ジ筒編機を用いて筒編後、２種のサンプ
ルを下記の同一酸性染料浴で９０°Ｃ４５分間染色しＬ
、ａ ＊ ｂ ｆｆｌを測定した。Next, after knitting with a 36-gauge tubular knitting machine, the two samples were dyed in the same acid dye bath shown below at 90°C for 45 minutes.
, a * b ffl were measured.
０酸性染料浴
グリーン染料・Ｔｅｃｔｉｌｏｎ Ｙｅｌｌｏｗ ４Ｒ
Ｏ，１χｏｗｔ−Ｔｅ１ｏｎ Ｒｅｄ ＦＲＬＬ
Ｏ，０２％ｏｗｔ・Ｔｅｃｔｉｌｏｎ Ｂｌｕｅ ６Ｇ
Ｏ１１４Ｘｏｗｔ−７ボラ７ ＡＶ ２．
０ ％ｏｗｔ浴比１ ： １００ ＰＨ６，５（第一リ
ン酸ソーダー第ニリン酸ソーダで調整）、結果を表−３
（４）に示す。0 acid dye bath green dye Tectilon Yellow 4R
O,1χowt-Te1on Red FRLL
O, 02%owt・Tectilon Blue 6G
O114Xowt-7 Bora 7 AV 2.
0% owt bath ratio 1:100 PH6.5 (adjusted with monobasic sodium phosphate and dibasic sodium phosphate), the results are shown in Table 3
Shown in (4).
尚、Ｌ、ａ、ｂ値は、日本重色工業ｆｍＯＰＴＩｃＡＬ
ＳＥＮＳＯＲＺで測定した。In addition, L, a, b values are Nihon Heavy Industries fmOPTIcAL
Measured with SENSORZ.
この表−３から明らかなように、本発明によれば、ポリ
アミドの［η］低下をおさえつら、末端アミノ基量を減
少させ、末端カルボキシル基量を増加させる。この結果
、酸性染料に対するＬ値を増加させ、著しい淡染化を示
すことが認められる。As is clear from Table 3, according to the present invention, the amount of terminal amino groups is decreased and the amount of terminal carboxyl groups is increased while suppressing the decrease in [η] of polyamide. As a result, it is observed that the L value for acidic dyes increases and the dyeing becomes significantly lighter.
Claims (2)
リアミドに、二官能Ｎ−アシルラクタムを添加して溶融
反応させることにより、下記（III）式を満足するポリ
アミドに変性することを特徴とする末端カルボキシル基
量の増加したポリアミドの製造方法。 −２０≦Ｃ＿Ｎ＿Ｈ＿２−Ｃ＿Ｃ＿Ｏ＿Ｏ＿Ｈ≦２０（
I ）０．０５≦ポリアミドの水分率（Ｗ％）≦０．４
（II）Ｃ＿Ｃ＿Ｏ＿Ｏ＿Ｈ−Ｃ＿Ｎ＿Ｈ＿２≧３０（I
II）（ここで、Ｃ＿Ｎ＿Ｈ＿２、Ｃ＿Ｃ＿Ｏ＿Ｏ＿Ｈは
各々グラム・当量／１０＾６グラム単位とする末端アミ
ノ基量、末端カルボキシル基量を表わす）(1) A polyamide that satisfies the following formula (I) and (II) at the same time is modified into a polyamide that satisfies the following formula (III) by adding a bifunctional N-acyllactam and causing a melt reaction. A method for producing a polyamide having an increased amount of terminal carboxyl groups. −20≦C_N_H_2−C_C_O_O_H≦20(
I) 0.05≦Moisture content of polyamide (W%)≦0.4
(II) C_C_O_O_H−C_N_H_2≧30(I
II) (Here, C_N_H_2 and C_C_O_O_H represent the amount of terminal amino groups and the amount of terminal carboxyl groups, respectively, in units of gram equivalent/10^6 grams)
末端基量に対し当量以上用いる特許請求の範囲第（１）
項記載の末端カルボキシル基の増加したポリアミドの製
造方法。(2) Claim No. 1 in which the bifunctional N-acyl lactam is used in an amount equivalent to or more than the amount of amino terminal groups of the polyamide.
A method for producing a polyamide having an increased number of terminal carboxyl groups as described in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6197788A JPH0627192B2 (en) | 1988-03-17 | 1988-03-17 | Process for producing polyamide with increased amount of terminal carboxyl groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6197788A JPH0627192B2 (en) | 1988-03-17 | 1988-03-17 | Process for producing polyamide with increased amount of terminal carboxyl groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01236238A true JPH01236238A (en) | 1989-09-21 |
| JPH0627192B2 JPH0627192B2 (en) | 1994-04-13 |
Family
ID=13186748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6197788A Expired - Fee Related JPH0627192B2 (en) | 1988-03-17 | 1988-03-17 | Process for producing polyamide with increased amount of terminal carboxyl groups |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0627192B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996034909A1 (en) * | 1995-05-04 | 1996-11-07 | Dsm N.V. | High-molecular polyamide |
| WO1998047940A1 (en) * | 1997-04-22 | 1998-10-29 | Dsm N.V. | High-molecular polyamide |
| DE102007040683A1 (en) | 2007-08-29 | 2009-03-05 | Evonik Degussa Gmbh | Sheathed pipe |
| DE102008044224A1 (en) | 2008-12-01 | 2010-06-02 | Evonik Degussa Gmbh | Use of a composition for contact with supercritical media |
| DE102009001001A1 (en) | 2009-02-19 | 2010-09-02 | Evonik Degussa Gmbh | Use of a conduit for the production of a pipeline laid in the water |
| DE102011007104A1 (en) | 2011-04-11 | 2012-10-11 | Evonik Degussa Gmbh | Polyamide sheathed steel construction tubes for offshore structures |
| JP2013540192A (en) * | 2010-10-25 | 2013-10-31 | ディーエスエム アイピー アセッツ ビー．ブイ． | Polymer composition, process for producing the composition and articles obtained from the composition |
| US8927737B2 (en) | 2011-08-09 | 2015-01-06 | Basf Se | Process for purifying ionic liquids |
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1988
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996034909A1 (en) * | 1995-05-04 | 1996-11-07 | Dsm N.V. | High-molecular polyamide |
| BE1009365A3 (en) * | 1995-05-04 | 1997-02-04 | Dsm Nv | High-molecular polyamide. |
| WO1998047940A1 (en) * | 1997-04-22 | 1998-10-29 | Dsm N.V. | High-molecular polyamide |
| DE102007040683A1 (en) | 2007-08-29 | 2009-03-05 | Evonik Degussa Gmbh | Sheathed pipe |
| DE102008044224A1 (en) | 2008-12-01 | 2010-06-02 | Evonik Degussa Gmbh | Use of a composition for contact with supercritical media |
| WO2010063506A1 (en) | 2008-12-01 | 2010-06-10 | Evonik Degussa Gmbh | Use of a composition for the contact with supercritical media |
| DE102009001001A1 (en) | 2009-02-19 | 2010-09-02 | Evonik Degussa Gmbh | Use of a conduit for the production of a pipeline laid in the water |
| JP2013540192A (en) * | 2010-10-25 | 2013-10-31 | ディーエスエム アイピー アセッツ ビー．ブイ． | Polymer composition, process for producing the composition and articles obtained from the composition |
| DE102011007104A1 (en) | 2011-04-11 | 2012-10-11 | Evonik Degussa Gmbh | Polyamide sheathed steel construction tubes for offshore structures |
| EP2511430A1 (en) | 2011-04-11 | 2012-10-17 | Evonik Degussa GmbH | Steel tubes for offshore structures |
| US8927737B2 (en) | 2011-08-09 | 2015-01-06 | Basf Se | Process for purifying ionic liquids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0627192B2 (en) | 1994-04-13 |
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