TW498092B - Preparation of diimide-diacid and polyamide-imide containing hydroxyl group - Google Patents

Abstract

Described herein are polyamideimides derived from new diimide-diacid containing hydroxy group. These polymers have excellent solubility combined with good mechanical performance, high heat resistant, and further modification. The polymers are processable and high performance engineering plastics.

Description

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 498092 A7 B7 V. Description of the invention (\) (1) Background of the invention: Aromatic polyamidoamine imine has excellent heat resistance, mechanical properties, and ten chemical properties and electrical insulation It is a high-performance, high-performance polymer material that is widely used in electrical and electronic parts, automotive parts, and general mechanical parts. However, up to now, there are still some problems in the processing of aromatic polyimide and imine. Compared with the previous general-purpose engineering plastics, the melting temperature of aromatic polyamidamine and imine is higher, and it is easy to gel when heated and melted at high temperature. Therefore, it cannot be processed by melt molding. (Heating polyimide and imine to 320 ~ 350 ° c and pressing under pressure of 150 ~ 300 Kg / cm] is considered as a material that is not easy to form. In addition to poor melting properties, the solubility of aromatic polyamidoamines is generally poor, although polyamidoamines can also be used directly after polymerizing monomers in solvents (for example, JP 44,19274). That is, varnish type is used for coating purposes, but these varnishes need to use highly polar solvents that do not contain active hydrogen such as mouth ratio, mouth ratio and N-fluorenyl-2- mouth ratio ketone (NMP) or N, N-di Solvents such as fluorenylacetamide (DMAc). This varnish has storage problems, and once exposed to moisture, it will become cloudy and suspected of gelling. In addition, these polar solvents of inactive hydrogen are expensive, which limits the practicality of the varnish industry. In order to solve the problem of solvent use, some patents (such as JP 5123999, JP 5617374, JP 5622330, JP 5634210) proposed the use of phenol solvents. 4- The paper size applies the Chinese National Standard (CNS) Λ4 specification (210X29? Mm) ) (Please read the notes on the back before filling this page)

、 1T 498092 A7 ____B7 V. Description of the invention (z) The polar solvent which replaces inactive hydrogen is made into varnish. It is also worth noting that up to now, polyimide fluorimide film products are very limited, the main reason is the poor solubility of polyamidamine imine. The method for preparing feamine imine is to use polycondensation of tnmelhtic anhydride and diamine, but it is not easy to make high molecular weight linear polyamidoimine by this method. . The improved method is to first activate stupid trimellitic anhydride into 4-'chloroformyl phthalic anhydride and then perform condensation reaction with diamine at low temperature to form polyamide-amic acid. , And then baked by coating or high temperature thermal closed-loop method. However, this preparation procedure has many shortcomings. First, the activation of trimellitic acid raises the cost of the process, and the activated 4-fluorene gas anhydride is unstable and easily hydrolyzed. Second, the polyamidoamine-pyramidate produced by low-temperature polycondensation contains strong acid (HC1) as a by-product. Direct hot roasting or cyclization in a high-temperature solvent will destroy the amidinide bonds and cause a decrease in molecular weight. In order to solve these shortcomings, there is a patent report that a trimellitic anhydride and a diamine are first reacted to form diimide-dicarboxyHc acid, and then activated to form dihydrazine chloride, and then a low-temperature polycondensation reaction is performed. However, this method is costly and the diacid gas compound is not easy to purify. Later, although it was discovered that diisocyanate can be heated with trimellitic acid needles or derivatives thereof to obtain polyamidamine and imine, the types of diisocyanate are limited and difficult to store. Therefore, how to prepare polyimide and imine by a simple and low-cost method is one of the important topics today. • 5 · This paper size applies the Zhongguanjia Standard (CNS) Λ4 specification (21GX297 mm) — »^ ϋ— —m imMU 0 —, _ _ installed-(Please read the precautions on the back before filling in this Page) Order Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Α7

V. Description of the invention (3) In the literature (Malinge et al ·, Brit · Polym · J ·, vol · 20, ρ 4j1 (1988)), it is reported that the introduction of warp groups into the molecular chain of polyimide can improve the polymer Mutual attractiveness with solvents, which in turn improves the solubility of polyimide. Furthermore, the polymer containing a hydroxyl group is a functional polymer, and the polymer molecules can be cross-linked by the hydroxyl group, or the polymer can be modified by introducing other functional groups through the hydroxyl group. The object of the present invention is to prepare a soluble and easily modified polyamidamine and imine by a simple and inexpensive method. The invention discloses a novel hydroxyl-containing diammonium imide dicarboxylic acid compound. Using this compound and different diamine compounds, a condensation agent triphenyl phospite is used for direct polycondensation, and a series of polymerization can be obtained. A new type of polyamidamine / imine resin containing hydroxyl groups. HLH 11- -II nm ftm —ϋ —ϋϋ ml —an in (Please read the precautions on the back before filling out this page) Order the standard printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs to print the appropriate standard for each country. One foot of paper "Extreme | centimeter 498092 A7 B7 V. Description of the invention (4) (2) Summary of discovery: The present invention discloses a hydroxyl-containing diamidine dicarboxylic acid compound (I), polyamidamine and imine In the preparation method, these polymers have excellent solubility, processability, thermal stability, and mechanical strength. These polymers are obtained by polycondensation of a hydroxydifluorene imine dicarboxylic acid compound and different diamine compounds. The chemical structure of hydrazone imine dicarboxylic acid (I) is:

COOH 99.9 (I) Polydiamine imine polymers containing various hydroxyl groups can be obtained by performing a polycondensation reaction between this diamimine dicarboxylic acid compound and different diamine compounds. Amine imine has the following general structure:

£ ^ 9 -—r ^ -nc Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) where Ri stands for: 敎 观 加 义 -7- This paper standard applies to Chinese national standards (CNS) Λ4 specification (210X 297 mm) 498092 A7 B7 V. Description of the invention

(Please read the notes on the back before filling this page)

Printed by the Consumer Co-operation of the Central Standards Bureau of the Ministry of Economic Affairs JQr < yJ ^-^ y ^ Qr ch3

HX < 〇) -〇CH2CH2〇 < P ^^ 〇CH2CH2〇 · ^ or 6 CH ^ ^ -〇CH2CH2〇hQ > ^-< ^ 〇cH2CH2〇- < 0 ^ 8- This paper size is applicable Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 498092 A7 B7 _V. Description of the invention ((〇) (3) Detailed description of the discovery: The diphenylimide-dicarboxylic acid compound containing ceramidine diimide disclosed in the present invention The name is N, Nf-bis (4-carboxyphenyl) -phenylfluorenyl-3,3'A cardiotetracarboxydidonimine (N, N'-bis (4-carboxyphenyl) -benzhydrol-3, 3 ', 4,4'-tetracaitoxydUmide), this hydroxyl-containing diimide dicarboxylic acid compound (I) is composed of 3,3', 4,4L phenylhydrazone-tetracyl-diacid needle with 2 times Mol-numbered amino-benzoic acid is obtained by reaction in glacial acetic acid. The reaction formula is shown below.

one CM0 V

OHIC—H

〇 \ b " H2I 2

-C〇〇H (Please read the precautions on the back before filling out this page) glacial acetic acid HOOC ^ P ^ N:

〇 | 1

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the hydroxyl-containing polyamidoamine imine disclosed by the present invention is composed of a hydroxyl-containing-acidimine diene acid compound (I) and different diamine compounds in the presence of a condensing agent. It is obtained by direct polycondensation. One of the most suitable condensing agents is a mixed solution of triphenyl ph9Spite (TPP) and pyndine (py). We can use polar solvents, such as N-methyl-2-NMP, and salts such as potassium chloride or calcium carbonate (CaCb), which do not contain active hydrogen. -This sheet scale is applicable to the national standard (CNS) M specification (nos7 male I) 498092 A7 B7 V. Description of the invention (1) Polyacrylamide imine is prepared by polycondensation reaction. The chemical reaction is shown below.

-C〇〇H + h2N-R1-NH2

0 H ~ Camp Π (Please read the notes on the back before filling this page) Among them, the groups represented by 1 ^ are:

H〇3SS〇3H,, H3CCH3? Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

-10- This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 498092 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (δ) CH3-^ 〇 > -〇 -^ 〇 ^^ > -〇 ^ 〇 > -h3c, 〇 ^ 〇K) CH2CH2〇 < 0 ~ ^ > -〇CH2CH2〇hQ ^ or ft CH- ^ -〇CH2CH2〇-^^ H0- 〇CH2CH2〇- < P >-^^ 3. Hereinafter, examples of the preparation of the diamidine dicarboxylic acid compound (I) and the polyamidamine imidate of the present invention will be described in detail. Example 1 Synthesis of a diammonium imide dicarboxylic acid compound [N, N'_bis (4-carboxybenzyl) -benzylmethanyl-tetrakisyl ii. Lan Yayuean] (I) will be 14.5 3,3 \ 4,4 phenylbenzyl-tetracarboxy-dianhydride, 12.2 g of p-aminobenzoic acid dissolved in 30 ml of glacial acetic acid, and it will turn yellow after stirring at 100 ° C for 2 hours Precipitation of solids, and then reacting 1 small -11-This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 cm) (Please read the precautions on the back before filling out this page) • I pack · " T " Order 498092 A7 B7 5. Description of the invention (° |) After that, the solid is filtered and washed several times with ethanol to obtain a light yellow solid (I). The melting point was 373 ° C, and the yield was 85%. Infrared spectrum shows that the characteristic absorption peaks of fluorene imine group are at the positions of 1768 and 1710 cnr1, and the absorption peaks of carboxylic acid group are at the positions of 1688 and 3380 cmf1. Elemental analysis: Theoretical value: C, 66.19%; H, 3.23%; Ν, 4.98 〇 / 〇; Analytical value: C, 66.63%; Tritium, 3.46%; Ν, 4.84%. Example 2 Preparation of a Novel Polyfluorene from Diamidimide Diazylic Acid Compound (I) and 3,3,5,5f-u ^ yl_2,2_bis [4_ (4-aminebenzyl) benzyl] propane The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed 4.22 grams of N, Nf-bis (4-carboxyphenyl) -phenylfluorenyl-3,3,4,4L tetracarboxydiamidoimine, 3.49 grams 3,3 ', 5,5'-tetrafluorenyl-2,2_bis [4_ (4-aminebenzyloxy) phenyl] propane (3,3f, 5,5f-tetramethyl-2,2-bis [4- (4-aminophenoxy) phenyl] propane) »2.5 g of calcium chloride, 6 ml of triphenyl phosphite and 6 ml of mouth ratio σ fixed and 20 liters of N-methyl-2-port Each ketone was added to the reaction flask, and reacted at 1000 hours for 2 hours. After the reaction is completed, the mixture is poured into methanol and then killed, and a filamentous precipitate is obtained. The inherent viscosity of this polyamidoamine imine in N, N-diamidoacetamido is O.SQdLg-1 (the solution concentration is O.SgdL · 1, measured -12- Zhongguanjia standard applies to this paper size (CNS) A4 specification (21GX 297 ~~, description of the invention (L0)! Temperature is 30 ° C). In the infrared spectrum, the characteristic absorption peaks of amido groups appear at 3307 cm · 1 and 1662 cm · 1; Basic absorption = at the positions of 1771 cm 1 and 1710 cm_i. This polymer is dissolved in N, N-dimethylacetamidamine, poured into a glass dish, and then dried to remove the dissolved back 1J, which is transparent and strong. Tough film. Mechanical properties of the film: · 103 MPa · Elongation: 6%; Tensile modulus: 2.7 GPa. / Valley properties · This polymer is soluble in N-methyl-2-port ratio Oral ketones (NMP), N, N-dimethylacetamide (DMAc), N, dimethylmethazine (DMF), dimethyl stilbene (DMSO), meta-fluorenylphenol, butyl Lactone, Cyclohexanone, Orbital and Tetrahydrocyclopentanone, etc. Thermal properties: Glass transition temperature: 285 ° C; Temperature of cracking 10% under nitrogen: 487.0; Cracking under air 10 Temperature of%: 488. (: 800 under nitrogen The residual amount: 64% having the structure:

H? C

OH ~-< 〇 > -CN- Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economy-13 This paper size is applicable to China National Standards Corporation (CNS) Λ4 specification (210 X 297 mm (please read the precautions on the back first) (Fill in this page again)

Claims (1)

498092 ψ Η θ Amended on June 27, 2001 6. Scope of patent application m ό. 2U… ..... Vf tK A kind of mesityl-containing diimide dicarboxylic acid compound (I) 1 whose structure is as follows: HOOC ^ > X ^ HCOCH ⑴-A method for preparing a hydroxyl-containing dimethylimine dicarboxy hydrazone compound ⑴, which consists of a pair of 3,3 ·, 4,4, benzylidene-tetracarboxy-dicarbanhydride and 2 times the mole number. ·· Aminopyrazine is dissolved in glacial acetic acid k and reacts at 3 ° C and 10 ° C. A kind of polyamine with the following formula Play mm (Please read the notes on the back before filling this page) H ^ C cm ^ n 1 · — n —Bi n VI ϋ— 十 ', n I mKmm mmmmmm n I ni uc ^ r Printed by the Consumer Cooperative of the Property Bureau 4.—A method for preparing hydroxyl-containing polya & amine imine ) And various diamine compounds in the presence of calcium sulfide, tribenzyl succinate, ottEJ, and N- · methyl_2-〇 ratio; in the presence of ζ, t was reacted at 100 5C for 2 hours. The structure of the brewing iminium: -14- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)