JPH0229415A - Continuous production of polyamideimide - Google Patents

Abstract

PURPOSE:To obtain stably and continuously a polyamideimide by performing a continuous reaction of an acid component contg. a tricarboxylic acid monoanhydride, a dicarboxylic acid and a tetracarboxylic acid dianhydride with an org. diisocyanate component by using a multi-screw reactor. CONSTITUTION:An acid component contg. a tricarboxylic acid monoanhydride (e.g. trimellitic anhydride), a dicarboxylic acid (e.g. adipic acid) and a tetracarboxylic acid dianhydride (e.g. pyromellitic dianhydride) and an org. diisocyanate (e.g. 2,4-tolylene diisocyanate) are continuously fed in one or a plurality of multi-screw reactors 6 connected in series from storage tanks 2 and 3 at the same time, heated and reacted together without any solvent. The formed polyamidimide is cooled in a cooling tank 7 and pelletized by means of a pelletizer 8.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for continuously producing polyamideimide, and more specifically, by reacting an organic diisocyanate with a dicarboxylic acid or an acid anhydride, The present invention relates to a continuous solvent-free polymerization method for forming a polymer (polyamideimide) containing amide bonds and imide bonds.

[Conventional technology]

Organic diisocyanates and dicarboxylic acids and! ! The polyamide-imide obtained by the reaction of 2m hydrate and its manufacturing method are disclosed in Japanese Patent Application No. 123394/1982.

However, the above literature only describes a method for producing polyamideimide batchwise.

This batch method has high manufacturing costs and unstable product quality, and cannot be said to be an industrially advantageous method.

Furthermore, a method for producing polyamide semi-continuously or continuously from organic diisocyanate and dicarboxylic acid is known (Japanese Patent Application Laid-open No. 59-80422.59-80423).
. However, this publication does not contain any description of a method for producing polyamide-imide, and it is difficult to produce polyamide-imide using this method.

The object of the present invention is to provide a method for continuous production.

[Means to solve the problem]

The present inventors conducted intensive studies on a method for industrially stably producing polyamideimide, and as a result, tricarboxylic acid monoanhydride (A) and dicarboxylic acid (B) were obtained.

Among tetracarboxylic acid dianhydrides (C) and organic diisocyanates (D), 111 or more types of acids A to C containing at least one type of paraboloids and D
Reaction with one or more of the ingredients.

By conducting the process continuously in the absence of a solvent using one or more multi-screw reactors connected in series, an industrially advantageous and stable quality production method for polyamide-imide has been completed.

The first step in the production reaction of polyamideimide is CO2
It is thought that this is a reaction in which a polymerization reaction proceeds and ends as a second step. The reaction intermediate of this reaction has extremely strong adhesion to metals, and uneven mixing causes gel-like substances in polyamide-imide products. Therefore, as the reactor used in the present invention, it is preferable to carry out the reaction using a multi-screw reactor having a self-cleaning screw including a kneading block. In order to remove CO2 in the first half of the entire reactor, it is also preferable to provide a vent hole in a part of the bottom feed screw and to suck it in with a vacuum pump if necessary. In order to accelerate the reaction and obtain polyamide with less gel-like substances, the screw rotation speed should be lower.
It is necessary to rotate and mix at a high speed of pm or higher, preferably 200 rpm or higher. Further, it is preferable that the proportion of the kneading block occupies a portion of the entire screw. If it is less than 10, there is insufficient mixing and there is a lot of gel-like material. On the other hand, if it is 50% or more, the reaction product will be absorbed,
The desired product cannot be obtained because extrusion is difficult and CO2 is not removed sufficiently.

Each reactor requires a reactor that can independently control the reaction temperature in five or more sections, and the temperature in each section is calculated as follows:
The range from T+20) to (T+70)'C is preferred. (T
If the reaction temperature is lower than +20)'C, the reactants will not melt and flow sufficiently, and therefore sufficient mixing will not take place, making it impossible to obtain polyamide-imide with less gel-like material.

If the temperature is higher than (T+70)'C, thermal decomposition begins, and therefore products with excellent physical properties cannot be obtained. The flow start temperature referred to here is the temperature at which fluidity begins to be seen with the naked eye.

The organic diisocyanate component used in the present invention is not particularly limited, and representative examples include 4
, 4-diphenylmethane diisocyanate, 2.4-)
lylene diisocyanate, 2,6-lylene diisocyanate, phenylene diisocyanate, 1,5-naphthylene diisocyanate, a,a-cyclo-4,4-cyphenylmethane), xylylene diisocyanate Isocyanate, aromatic diisocyanate having 8 to 20 carbon atoms such as tetramethylxylylene diisocyanate, and 8 to 20 carbon atoms such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, etc. aliphatic or alicyclic diisocyanates. In consideration of mechanical properties and heat resistance, aromatic diisocyanates are preferred, and 4 is particularly preferred.
, 4-diphenylmethane diisocyanate, 2.4-)
Lylene diisocyanate, 2,6-lylene diisocyanate is used.

In addition, the dicarboxylic acid component is not particularly limited,
One or more selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and both-terminated carboxylic acid polyesters can be used.

Typical dicarboxylic acids include aliphatic dicarboxylic acids having 4 to 54 carbon atoms such as glutaric acid, adipic acid, azelaic acid, pimelic acid, sebacic acid, decanniic acid, dodecanniic acid, dimer acid, and isophthalic acid, terephthalic acid,
8 to 20 carbon atoms such as phthalic acid and naphthalene dicarboxylic acid
aromatic dicarboxylic acids. Among these low molecular weight dicarboxylic acids, aliphatic dicarboxylic acids are more preferably used than aromatic dicarboxylic acids from the viewpoint of moldability.

Examples of the double-terminated carboxylic acid polyester include polyhexane adipate dicarboxylic acid, polyhexane azelate dicarboxylic acid, poly 3-methyl-1,5-pentanediol adibate dicarboxylic acid, poly 3-nonal-1
．． 5-bentanediol azelate dicarboxylic acid, poly 2-methyl-1,8-octanediol adipate dicarboxylic acid, poly 2-methyl-1,8-octanediol azelate dicarboxylic acid, poly 1,9-nonanediol adipate dicarboxylic acid , poly 1,9-nonanediol azelate dicarboxylic acid, poly 2-methyl-1,8-octanediol/1.9-nonanediol adipate dicarboxylic acid, poly 2-methyl-1,8-octanediol/1.9 - Aliphatic polyester dicarboxylic acids such as nonanediol azelate dicarboxylic acid, aromatic dicarboxylic acids such as polyethylene terephthalate dicarboxylic acid, polybutylene terephthalate dicarboxylic acid, and β-
The release of one or more lactones such as propiolactone, vivalarolactone, γ-valerolactone, ε-caprolactone, methyl-ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, and δ-caprolactone. Examples include polyester dicarboxylic acids derived from ring polymers.

In the present invention, in order to obtain a product with particularly excellent hydrolysis resistance, 3-methyl-1,5-bentanediol, 2
- It is preferable to use diols such as methyl-1,8-octanediol and 1,9-nonanediol alone or in combination, especially 2-methyl-1,8-octanediol t
- If selected, the low-temperature properties are also significantly improved, which is desirable.

These diols account for 10 mol or more of the total diol components,
It is preferably used in a proportion of 30 mol % or more, more preferably 50 mol % or more. In addition, particularly good hydrolysis resistance can be obtained by using a polyester obtained by ring-opening polymerization of a lactone monomer containing 30 moles or more of β-methyl-δ-valerolactone as the carboxylic acid polyester at both ends. Therefore, it is preferable.

The above-mentioned double-terminated carboxylic acid polyester can be obtained by a conventionally known method for producing polyester. for example,
A polyester diol having hydroxyl groups at both ends obtained by polycondensing an excess amount of a dicarboxylic acid component with a diol component and by ring-opening polymerization of a lactone using a compound having active hydrogen such as ethylene glycol as an initiator. can also be reacted with dicarboxylic acid or its anhydride to obtain a double-terminated carboxylic acid polyester.

As the dicarboxylic acid component used in producing polyamide-imide in the present invention, it is preferable to use an aliphatic dicarboxylic acid and a double-terminated carboxylic acid polyester in combination, considering the moldability and flexibility of the resulting polyamide-imide. Furthermore, it is preferable that 10 moles or more of the carboxylic acid polyester at both ends is contained as dicarboxylic acid in 100 moles of the dicarboxylic acid component.

The molecular weight of the carboxylic acid polyester at both ends is 300 to s.
, ooo is preferable, more preferably 500 to
5,000. If the molecular weight is less than 300, the molding processability will deteriorate, and if it exceeds s, ooo, the mechanical properties and transparency will deteriorate, which is not preferable.

The acid anhydride used in obtaining the polyamideimide of the present invention is particularly limited as long as it is tricarboxylic acid monoanhydride or tetracarboxylic acid dianhydride used in the production of conventionally known polyimide or polyamideimide. There isn't.

As an acid anhydride of tricarboxylic acid, trimellidic acid anhydride,! Preferred compounds include intramolecular anhydrides of aromatic tricarboxylic acids having 9 to 20 carbon atoms, such as 2,3-benzenetricarboxylic anhydride.

Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, diphenyl-3,3', 4,4'-tetracarboxylic dianhydride. , diphenyl-2,z: 3.3-
Tetracarboxylic dianhydride, naphthalene-2,3,6゜7-tetracarboxylic dianhydride, naphthalene-1゜2,
4.5-tetracarboxylic dianhydride, naphthalene-1,
4,5,8-tetracarboxylic dianhydride, decahydronaphthalene to 1.4.5.8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene - 1.2.5.6-tetracarboxylic dianhydride, 2,6-cyclonaphthalene - 1.4.5.
8-Tetracarboxylic dianhydride, 2,7-cyclonaphthalene-1.4.5.8-tetracarboxylic dianhydride, 2
, 3.6.7-titrachloronaphthalene-1.4.5.
8-tetracarboxylic dianhydride, phenanthrene-1゜3, 9.10-tetracarboxylic dianhydride, perylene-
3,4,9,10-tetracarboxylic dianhydride, bis(
2,3-dicarboxyphenyl)methanihydride, bis(3,4-dicarboxyphenyl)methanihydride, 1
．． 1-bis(2,3-dicarboxyphenyl)ethane dihydride, 1.1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2.2-bis(2,3-dicarboxyphenyl) ) Propane 2m7FA'llJ, 2゜3
-bis(3,4-dicarboxyphenyl)propane dim
hydrate, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)
Etherni fR hydrate, ethylenetetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine- 2,3,4,5-tetracarboxylic dianhydride, vilasine-2,3,5゜6-tetracarboxylic dianhydride, thiophene-2゜3,4,5-tetracarboxylic dianhydride, benzophenone -3,3,4,
Preferred compounds include intramolecular dianhydrides of aromatic or aliphatic tetracarboxylic acids having 6 to 24 carbon atoms, such as 4-tetracarboxylic dianhydride.

In this reaction, the equivalent ratio of organic diisocyanate, dicarboxylic acid, and acid anhydride is preferably ([˜NC0)/(C˜, more preferably 0.95 or more and 1.03 or less.

Organic diisocyanate component (D), dicarboxylic acid component (B), tricarboxylic acid anhydride component (A), and tetracarboxylic acid dianhydride component (C) are all continuously molten liquid using a metering pump. directly supplied to the reactor. Any pump may be used as long as it has excellent metering performance, but gear pumps and multiple plunger pumps are preferred. (A)～
When using a plurality of components (C), they may be mixed in advance or may be supplied separately.

When producing polyamideimide according to the present invention, a suitable catalyst may be used to promote the reaction.

Furthermore, additives such as colorants, fillers, antioxidants, and ultraviolet absorbers, or lubricants may be added depending on the purpose.

〔Example〕

The present invention will be specifically explained below using Examples.

In the examples, "parts" represent "parts by weight." Note that ηinh was measured at 30°C in an NMP (N-methylpyrrolidone) solution containing 0.5% polyamideimide. Further, a specific example of a production diagram of the manufacturing method of the example is shown in Figure fJX1.

Example 1 99.8 parts of polyester dicarboxylic acid (cPMPA) with a nine-average molecular weight f1083 obtained from 3-methyl-1,5-bentanediol and adipic acid and 2 parts of 1-methyl-1-oxo-phospho2 were added to 70 Trimellidic anhydride (T
MAH) was kept warm at 190°C and <z), (at
and store them under a nitrogen gas atmosphere.

Separately, 4,4-diphenylmethane diisocyaner (MDI) was kept at 50° C., placed in a storage tank (1), and stored under a nitrogen gas atmosphere.

70'C (7) CPM=PA with rotation accuracy of ±2/1
Self-cleaning co-directional twin-screw reactor (a) (BP-30-8,
It was supplied to the Plastics Engineering Research Institute. Also, 19
0° C. tube 6 is a degassing port to remove all gases. A nozzle with a diameter of 3.0 mm was used for the reaction termination section. The reaction temperatures were as shown in Table 10.

were continuously supplied to the reactor at a rate of 28.29/min using a metering pump (4) with a rotation accuracy of ±2/1000, respectively.

The reactor is a self-cleaning co-rotating twin-screw reactor containing a kneading block, and the screw diameter is C.
D) is 30-, screw length (L) is 108011
It was JI. The proportion of the kneading block was 34%.

The reactor is divided into six sections, section 1 to section 6, respectively, from the raw material supply port. Section 3.4 is a degassing port (5) for removing CO2f, and the cefsyscrew rotation speed is
: 300 rpm The reaction was carried out under these conditions,
The polyamide-imide coming out of the reactor discharge part was cooled and solidified in cooling water and pelletized. The obtained polyamideimide had a yinh of 0.82 d/f.

Example 2 99°8 parts of polyester dicarboxylic acid (CPMPA) with an average molecular weight of 1083 obtained from 3-methyl-1,5bentanediol and adipic acid and 0.2 parts of 1-mesol-1-oxophosphorene were mixed at 70°C. It was placed in a storage tank equipped with a stirrer kept at ℃ and stored under a nitrogen gas atmosphere. Maku,
50 parts of azelaic acid (AZA) and 50 parts of trimellidic anhydride
The mixture was kept at 190° C., placed in a storage tank equipped with a stirrer, and mixed under a nitrogen gas atmosphere to form a completely transparent mixture.

CPMPA containing l-methyl-1-oquine-phosphorene
k5G, 9y/min, TMA)l-AZA
Mixture t13, Or/min, MD I wo 29.9 f
A polyamide powder was obtained in the same manner as in Example 1 except that the amount of polyamide was supplied per minute. The obtained polyamideimide had a ηinh of 0.80 d (1/l).

Example 3 29.9 parts of adipic acid (ADA) and 70.1 parts of trimellitic anhydride (TMAH) were placed in a storage tank equipped with a stirrer kept at 190°C, and mixed under a nitrogen gas atmosphere to form a completely transparent mixture. It was made into a mixture.

Polyester dicarboxylic acid (c) with average molecular weight 3) 1083
PMPA) 98.8 parts, l-methyl-1-oxo-phospho V 70.2 parts, Irganox 245 1.0
A polyamide-imide was obtained in the same manner as in Example 1, except that the mixture was fed to the reactor at 49.2 F/min, the ADA/TMAH mixture at 16.7 t/min, and the MDI at 34.1 P/min. 71nh of the obtained polyamideimide is 0.8
It was 6 dIj/ri.

〔Effect of the invention〕

According to the present invention, polyamideimide can be polymerized by an industrially advantageous method, that is, a continuous method under a hot solvent.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing a specific example of the manufacturing method of the present invention. 1: Incyanate storage tank 2: Polycarboxylic acid storage tank 3: Carboxylic acid, acid hydrate storage tank 4, <: 4: Metering pump 5: Degassing port 6: Reactor 7: Cooling tank 8: Pelletizer patent applicant Ri Co., Ltd. La Shi

Claims (5)

[Claims] (1) Among tricarboxylic acid monoanhydride (A), dicarboxylic acid (B), tetracarboxylic acid dianhydride (C), and organic diisocyanate (D), at least one of component A The reaction between one or more of the components A to C and one or more of the components D is carried out continuously using one or more multi-screw reactors connected in series. A method for continuously producing polyamideimide, characterized by: (2) The manufacturing method according to claim (1), wherein the dicarboxylic acid component contains a double-terminated carboxylic acid polyester having a molecular weight of 300 to 8,000 in a proportion of 10 mol% or more. (3) Claim in which the multi-screw is a self-cleaning co-rotating multi-screw that includes a kneading block (
The manufacturing method described in 1). (4) The manufacturing method according to claim (3), wherein the ratio of the kneading block to the total screw is 10 to 50%. (5) The reactor has independent temperature control sections consisting of at least five sections, and the temperature of each section is adjusted to the flow start temperature (T) of the reactant present in each section.
The manufacturing method according to any one of claims (1) to (4), characterized in that the temperature is controlled to be 20 to 70°C higher than the temperature (°C).