CN105254872B - A kind of Semi-aromatic transparent polyamide and its synthetic method containing pyridine heterocycle - Google Patents
A kind of Semi-aromatic transparent polyamide and its synthetic method containing pyridine heterocycle Download PDFInfo
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- CN105254872B CN105254872B CN201510779500.4A CN201510779500A CN105254872B CN 105254872 B CN105254872 B CN 105254872B CN 201510779500 A CN201510779500 A CN 201510779500A CN 105254872 B CN105254872 B CN 105254872B
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Abstract
The invention discloses a kind of Semi-aromatic transparent polyamide and its synthetic method containing pyridine heterocycle, with aliphatic diamine and 2 containing aromatic heterocycle, 6 pyridinedicarboxylic acids are raw material, polycondensation obtains a kind of Semi-aromatic transparent polyamide, the light transmittance of the polyamide has good heat resistance up to more than 90%.The transparent polyamide of the present invention is using aliphatic diamine and aromatic heterocycle dicarboxylic acids as raw material, method using the aqueous solution into salt and direct polymerization, obtain a kind of heterocycle Semi-aromatic transparent polyamide, this method is compared with the in general aqueous solution polymerize into salt, operating procedure is simplified, shortens the production cycle.
Description
Technical field
The present invention relates to a kind of Semi-aromatic transparent polyamide and its synthetic method containing pyridine heterocycle, and in particular to a kind of
With aliphatic diamine and 2, dipicolimic acid 2 is a kind of Semi-aromatic transparent polyamide containing heterocycle that raw material obtains.
Background technology
Polyamide is earliest application and current domestic and international application a kind of most widely thermoplastic engineering plastic.Because its is excellent
Physical and mechanical properties, it is especially noticeable to its transparent research, and semiaromatic transparent polyamide is except with excellent
Beyond the transparency, also with good heat endurance and dimensional stability etc., in optical instrument, precise part and high-grade physical culture device
The fields such as material are all widely used.
Study of synthesis method on Semi-aromatic transparent polyamide at present, concentrate on the aromatic series with dissymmetrical structure
The homopolymer of M-phthalic acid (or derivative) and diamine.
In addition, traditional semiaromatic polyamide composition synthetic method polymerize after being divided into salt, prepolymerization (polymerization) and solid phase
Deng three steps, commonly referred to as " two step method " or " three-step approach ", synthesis step is more, complex operation, production cycle length, waste discharge
It is more, it is unfriendly to environment.
The content of the invention
It is an object of the invention to overcome more synthesis step present in existing synthetic technology, complex operation, production cycle
Long, the shortcomings of waste discharge is more, unfriendly to environment, and provide a kind of new semi-aromatic containing pyridine heterocycle transparent polyamides
Amine and its synthetic method, " one-step method " technique by the aqueous solution into salt direct polymerization, streamline operation, shorten production week
Phase, and it is environmentally friendly by medium of water.With aliphatic diamine and 2, dipicolimic acid 2 is raw material, straight into salt through the aqueous solution
Connect polymerization and obtain a kind of Semi-aromatic transparent polyamide for closing heterocycle.The 2 of the present invention, dipicolimic acid 2, only with a N atom
Instead of the C atoms in aromatic rings so that the symmetry of strand is further destroyed, and can obtain non-crystalline type polymer, and this is poly-
The light transmittance of acid amides has good heat resistance up to more than 90%.
The present invention is as follows to solve the technical scheme that its technical problem is taken：
A kind of method for synthesizing the Semi-aromatic transparent polyamide containing pyridine heterocycle, with aliphatic diamine and 2,6- pyridines
Dicarboxylic acids is raw material, it is characterised in that the synthetic method comprises the steps of：
(1) by 2, dipicolimic acid 2 is mixed in 200mL polymerization reaction kettle with water with 1: 3 mass ratio, and stirring is molten
Solution, then adds aliphatic diamine and antioxidant in polymerization reaction kettle, and inflated with nitrogen enters inert gas several times, makes in the lump
The inert gas pressure being finally filled with is 0-0.2MPa, and solution is protected using inert gas；
(2) step (1) products therefrom is heated in two stages in polymerization reaction kettle, is into the salt heating period first,
By heating response temperature adjustment to 40-60 DEG C, salting liquid is obtained under low pressure after (0-0.3MPa) stirring reaction 0.5-3h, is ensured former
The equimolar ratio of material, beneficial to the raising of polymerization stage molecular weight, then quick heating, makes temperature rise to 190-210 DEG C, polymeric kettle
Interior pressure rises to 1.2-2.4MPa, reacts 1-2h under this pressure and temperature state；
(3) polymerization reaction kettle is slowly deflated to normal pressure, is continuing to react 0.5-1h in the range of 200-220 DEG C, then
Discharging obtains the Semi-aromatic transparent polyamide containing pyridine heterocycle.
Preferably, step (1) described aliphatic diamine is C2-C14Aliphatic diamine, including：Ethylenediamine, butanediamine,
Hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 11 carbon diamines, 12 carbon diamines, 13 carbon diamines or 14 carbon diamines.It is excellent
Selection of land, the mol ratio of the heterocyclic pyridinium dicarboxylic acids and aliphatic diamine is 1: 1-1.05, preferably 1: 1.02.
Preferably, step (1) described antioxidant is KI, and the mass ratio of salting liquid and antioxidant is 1: 0.01.
Preferably, step (1) described inert gas is nitrogen, should at least 3 nitrogen of charge and discharge.
Preferably, step (2) the quick heating is that assigned temperature is heated in 0.5-1h.
Preferably, described slowly deflate of step (3) is that normal pressure is deflated in 1-2h, to obtain HMW polymerization production
Thing.
Preferably, the water is distilled water or deionized water.
According to another aspect of the present invention, according to semi-aromatic transparent polyamides of the above-mentioned synthesis containing pyridine heterocycle of the present invention
The method of amine, obtain a kind of Semi-aromatic transparent polyamide containing pyridine heterocycle, it is characterised in that the semi-aromatic is transparent poly-
The structural formula of acid amides is：
Wherein m is 0-12 integral multiple.
Compared with prior art, the notable beneficial effect and advantage that the present invention has are as follows：
The present invention is with aliphatic diamine and 2, and dipicolimic acid 2 is raw material, through being obtained into salt direct polymerization compared with high transparency
The semiaromatic polyamide composition containing pyridine heterocycle of performance, heat resistance suitable with the M-phthalic acid series transparent nylon transparency
Well, preparation method is simple, provides a kind of new component for the preparation of the transparent copolyamide of semi-aromatic, while the present invention exists
Medium is adopted water as in polymerization technique, it is environment friendly and pollution-free, and with making " one-step method " polymerization replace conventional " two step method " to polymerize, greatly
Technological process is simplified greatly, reduces waste discharge, shortens the operation cycle.
Brief description of the drawings
Fig. 1 is PA6PI and PA6I light transmission contrast schematic diagrams.
Fig. 2 is PA6PI diffraction light spectrogram.
Fig. 3 is the aerial weight-loss curve figures of PA6PI.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings, it is noted that described specific embodiment is only intended to
It is easy to the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1：
By the 2 of 20g (119mmol), dipicolimic acid 2 mixes with 60g water to be added in 200mL polymerization reaction kettle, is stirred
Dissolving is mixed, then 14.4g (124mmol) hexamethylene diamine and 0.02g KI are added in reactor, solution is well mixed, fills
Put nitrogen 3 times, last inflated with nitrogen to 0.1MPa, heating response temperature obtains salting liquid to 40 DEG C after stirring reaction 0.5h,
Pressure in 190 polymeric kettles is heated in 0.5h and rises to 1.5MPa, 1h is reacted in this case, is then slowly deflated in 1h
To normal pressure, then continue at 200-210 DEG C after reacting 0.5h, discharging, that is, obtain non-crystalline type polymer containing pyridine heterocycle
Semi-aromatic transparent polyamide PA6PI, its structural formula areFrom the structural formula
As can be seen that PA6PI prepared by the present invention only replaces the C atoms in aromatic rings with a N atom so that the symmetry of strand
Further destroy.Gained Semi-aromatic transparent polyamide PA6PI testing partial performances are as shown in Figures 1 to 3.
Embodiment 2：
By the 2 of 20g (119mmol), dipicolimic acid 2 mixes with 60g water to be added in 200mL polymerization reaction kettle, is stirred
Dissolving is mixed, then 20.6g (120mmol) decamethylene diamine and 0.01g KI are added in reactor, solution is well mixed, fills
Put nitrogen 3 times, last inflated with nitrogen to 0.1MPa is heated to 50 DEG C of reaction temperature, salting liquid is obtained after reacting 1h, in 0.5h
200 are heated to, pressure rises to 1.8MPa in polymeric kettle, reacts 1h in this case, is then slowly deflated in 1h often
Pressure, continue to discharge after reacting 1h at 210-220 DEG C, that is, it is transparent to obtain semi-aromatic of the non-crystalline type polymer containing pyridine heterocycle
Polyamide PA10PI, its structural formula areThis is can be seen that from the structural formula
Invent the PA10PI prepared and the C atoms in aromatic rings are only replaced with a N atom so that the symmetry of strand is further broken
It is bad.
Embodiment 3：
By the 2 of 20g (119mmol), dipicolimic acid 2 mixes with 60g water to be added in 200mL polymerization reaction kettle, is stirred
Dissolving is mixed, then adds 24.4g (122mmol) 12 carbon diamines and 0.01g KI in reactor, makes solution mixing equal
It is even, charge and discharge nitrogen 3 times, last inflated with nitrogen to 0.2MPa, 50 DEG C of reaction temperature is heated to, salting liquid is obtained after reacting 1h,
210 DEG C are heated in 1h, pressure rises to 2.1MPa in polymeric kettle, reacts 1h in this case, is then slowly put in 1h
Gas continues to discharge after reacting 1h at 210-220 DEG C, that is, obtains semiaromatic of the non-crystalline type polymer containing pyridine heterocycle to normal pressure
Race transparent polyamide PA12PI, its structural formula areCan be with from the structural formula
Find out, PA12PI prepared by the present invention only replaces the C atoms in aromatic rings with a N atom so that the symmetry of strand is entered
One step is destroyed.
Compared with polyamide compare, the light transmittance of Semi-aromatic transparent polyamide and heat resistance prepared by the present invention is equal
It is significantly increased, table 1 shows semiaromatic transparent polyamide PA6PI, PA10PI, PA12PI prepared by the embodiment of the present invention 1~3
With the contrast of existing polyamide such as PA6I, TROGAMIDCX9710 partial properties index, it is not difficult to find out, the embodiment of the present invention 1
~3 semiaromatic transparent polyamide PA6PI, PA10PI, PA12PI prepared, its light transmittance reach more than 90%, and existing normal
The polyamide seen, its light transmittance are typically difficult to reach more than 90%, in addition, the semiaromatic transparent polyamide for preparing of the present invention compared with
Existing PA6I, TROGAMIDCX9710, its incipient degradation temperature and weightless 5% degradation temperature are higher, show this hair
The semiaromatic transparent polyamide of bright preparation has the heat resistance significantly improved.
Semiaromatic transparent polyamide prepared by the embodiment 1~3 of table 1 and existing polyamide portion performance indications
Compared with prior art, the present invention is with aliphatic diamine and 2, and dipicolimic acid 2 is raw material, through direct into salt
Polymerization obtains the semiaromatic polyamide composition containing pyridine heterocycle compared with high transparency energy, transparent with M-phthalic acid series transparent nylon
Property is suitable, and heat resistance is good, and preparation method is simple, and a kind of new group is provided for the preparation of the transparent copolyamide of semi-aromatic
Point, while the present invention adopts water as medium in polymerization technique, it is environment friendly and pollution-free, and replaced in the past with " one-step method " is polymerize
" two step method " polymerize, and enormously simplify technological process, reduces waste discharge, shortens the operation cycle.
More than, only the preferred embodiments of the present invention, the scope of protection of the invention are not limited thereto, any to be familiar with the skill
The people of art is being appreciated that the conversion or replacement expected disclosed herein in the range of, should all cover the scope in the present invention
Within, therefore, protection scope of the present invention should be defined by the protection domain of claims.
Claims (7)
- A kind of 1. synthetic method of the Semi-aromatic transparent polyamide containing pyridine heterocycle, with aliphatic diamine and 2,6- pyridines two Carboxylic acid is that raw material is synthesized, it is characterised in that the synthetic method comprises the steps of：(1) by 2, dipicolimic acid 2 is mixed in 200mL polymerization reaction kettle with water with 1: 3 mass ratio, stirring and dissolving, so Aliphatic diamine and antioxidant are added in polymerization reaction kettle in the lump afterwards, and are filled with inert gas several times, makes finally to be filled with Inert gas pressure be 0.1-0.2MPa, solution is protected using inert gas；(2) step (1) products therefrom is heated in two stages in polymerization reaction kettle,It is into the salt heating period first, by heating response temperature adjustment to 40-60 DEG C, stirring reaction under 0-0.3Mpa low pressure Salting liquid is obtained after 0.5-3h, ensures the equimolar ratio of raw material, beneficial to the raising of polymerization stage molecular weight,Followed by the polymerization heating period, temperature is quickly ramped up to 190-210 DEG C in 0.5-1h, pressure rises in polymerization reaction kettle 1.2-2.4MPa, react 1-2h under this pressure and temperature state；(3) polymerization reaction kettle is slowly deflated to normal pressure in 1-2h, continues to react 0.5-1h in the range of 200-220 DEG C, so Discharging obtains Semi-aromatic transparent polyamide afterwards, and the structural formula of the Semi-aromatic transparent polyamide is：Wherein m is any integer in 0-12.
- 2. synthetic method according to claim 1, it is characterised in that in step (1), the aliphatic diamine is C2- C14Aliphatic diamine, including：Ethylenediamine, butanediamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 11 carbon diamines, 12 carbon two First amine, 13 carbon diamines or 14 carbon diamines.
- 3. synthetic method according to claim 1, it is characterised in that the heterocyclic pyridinium dicarboxylic acids and aliphatic diamine Mol ratio be 1: 1-1.05.
- 4. synthetic method according to claim 3, it is characterised in that the heterocyclic pyridinium dicarboxylic acids and aliphatic diamine Mol ratio be 1: 1.02.
- 5. synthetic method according to claim 1, it is characterised in that in step (1), the antioxidant is KI, institute The mass ratio for stating salting liquid and antioxidant is 1: 0.01.
- 6. synthetic method according to claim 1, it is characterised in that in step (1), the inert gas is nitrogen, should At least 3 nitrogen of charge and discharge.
- 7. synthetic method according to claim 1, it is characterised in that the water is distilled water or deionized water.
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| CN112142963B (en) * | 2020-09-23 | 2024-03-22 | 武汉科技大学 | Biodegradable high molecular weight polyester synthesis method and application |
| CN114605631B (en) * | 2020-12-08 | 2024-03-12 | 台湾化学纤维股份有限公司 | Method for producing transparent polyamide copolymer |
| CN114409895A (en) * | 2022-01-07 | 2022-04-29 | 重庆沃特智成新材料科技有限公司 | Semi-aromatic polyamide and preparation method and application thereof |
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