TWI341851B - Precursor composition for polyimide and use thereof - Google Patents

Description

1341851 IX. Description of the invention: [Technical field to which the invention pertains] Compound #' abbreviated as ρι) precursor group This month also relates to the preparation and application of the composition in the brewing of imine. [Prior Art] The demand is getting higher and higher, while the traditional no ==== ί足3=: In some respects, it can make up for the traditional inorganic materials. (1) ^This ^DuPont's aromatic hybrid imine technology After the development, the text reached a wide range of touches, and the release of the pro-imine. Glare is used in industry. Polyurethanes are widely used in passivation films, stress buffers, protective masks, microelectromechanical and interlayer insulating films. Among them, the application as a protective coating for the integrated circuit element is a large-scale test because of the sinfulness of the integrated circuit component. However, the application of poly-imine is not only in the integrated circuit, but also in the construction, enameled wire, printed circuit board, sensing components, separation membrane and structural materials. Character. Generally, a polystaged imine is synthesized by a two-stage polymerization condensation reaction. It is suspended in the first stage to dissolve the diamine monomer such as hydrazine-methyl. Add a polar, aprotic bath to the polar, aprotic bath of bismuth qs^mp), dimethylacetamide (DMAC), dimethylformamide (dmf) or dimercaptoite (leg §〇) Almost the molar acid liver monomer. Thereafter, the condensation reaction is carried out at a low temperature or a normal temperature to form a polyimine precursor, i.e., poly(amic acid; abbreviated as PAA). 1341851. Then, in the second stage, the condensation dehydration cyclization reaction is carried out by a thermal imidiation or a chemical imidizati〇n, which is a polyamidoamide. The acid is converted to polyimine. The current reaction scheme for preparing polyimine can be briefly described as follows: Η 〇 〇〇ΛΛ〇 Π H2N-Ar, NH2 〇ΛαΛ-ν-hYVoh

Ar_i -H〇0 〇 0 'N.Ar N-Ar'-

Π Y 〇0 In the above preparation method, if the molecular weight of the polyamic acid obtained in the first stage is not determined (ie, the molecular weight is too small), after imidization, it is impossible to obtain a good physical property. A hybrid imine film. However, if the molecular weight of the (IV) aminic acid obtained in the first stage is too high, the viscosity thereof will be too large, so that the workability is deteriorated, and it is easy to have disadvantages such as poor leveling property. For example, in the spin coating, the convex and thick edges are not easy to level. In addition, when the too high polyamic acid molecule undergoes the second stage of imidization, the coated substrate is bent and deformed due to the interaction between the molecules and the internal force. Therefore, for the exemption, the second phase of the process has been extensively explored in the literature and the various methods of reducing the internal stress have been studied. The reasons for the leveling and internal stress are all due to the high molecular weight of the poly-araminic acid known in the first stage. In other words, if the amount of cover is used, it can provide a good physical property. ~Hungry amino acid 7 1341851 寐 and 'poly acid is quite suitable for moisture absorption, and then the poly-proline and water molecules should be reversed. For many years, it has continued to plague people engaged in the research of imine. The fineness of the material is as good as a fish and a bear's paw. The present invention is directed to the research and development, and the special synthesis method can provide the desired (4) ship with the desired physical properties in order to meet the needs of the industry. [Summary of the Invention]

It is an object of the present invention to provide a polyimide precursor composition comprising a phthalic acid oligomer having an ester group (_C(0)0R) and a carboxyl group (-C() at one end. The compound formed by the reaction of the dianhydride derivative of O) OH). Another object of the present invention is to provide a polyimine which is obtained by polymerizing a prepolymer composition of the present invention. [Embodiment] A polyimine precursor composition comprising:

(a) - a proline oligomer having the following formula (1)

(1); and L. -J m (b) - a compound of the following formula (2) 1341851

OH OR

OR OH (2); wherein ethylene git is a linear or branched ship having 1 to 14 carbon atoms, or GAG, which may be the same or different and each independently a tetravalent organic group;

P is a divalent organic group; m is an integer of 1 to 1 Å, preferably an integer of 5 to 5 Å; and wherein the molar ratio of the component (a) to the component (b) is 〇8: 1 to 1 2 : 1, preferably 0.9: 1 to 1.1: a linear group of 1 to 14 carbon atoms of the substituent R on the branch side

CH, and -ch3 where η is an integer from 0 to 1〇. By way of example and not limitation, the straight or branched alkyl group having one to one carbon atom may be methyl, ethyl, n-propyl, isopropyl, 1-methylpropyl, 2-methylpropyl, n-butyl, iso-yl, neobutyl, J•methylbutyl,

2-methylbutyl, county, hexyl, silk, or octyl f. R may also be independently an internal group, such as a 7' or ethylenically unsaturated group; the ethylenically unsaturated group is selected from the group consisting of: ethyl, propyl, ethyl, phenyl, Propyloxy 1341851 =, propyleneoxyethyl, propyloxypropyl, propyleneoxybutyl, propyloxy"oxyhexyl, methacryloxycarbonyl, methacryloxy a base, a propylene oxypropyl group, a methacryloxybutyl group, a decyl propylene oxypentyl group, a methacryloxyhexyl group, a group having the following formula (7), and the following formula (3) Group

R2 〇-CC-〇-R j-- (3), wherein R] is a phenyl, linear or branched CrC8 alkyl group, a linear or branched CrC8 stretching group, and a QQ stretching group. Or a straight or branched Ci_C8 hydroxyalkylene group; and r2 is hydrogen or a CrQ alkyl group.

Preferably, the substituents of the compound of the precursor composition are each independently CH5〇 〇 H2C=C-C-〇-C2H4-, H C=C-C-o-C2H4-

CHp I II H2C=C-C-〇-CH2-CH-CH2-

OH

H2C==C—C—O—CH2"CH-CH2—I I

H OH o

OH

10 0 1341851 ch3 ch3 -ch3 λ -ch2ch3 , -ch2ch2ch3 , ch3 , h2c—ch3

According to the present invention, the same or different tetravalent organic groups may be used, preferably each independently

Wherein each Y is independently hydrogen, halogen, CrC4 alkyl, or QQ perfluoroalkyl; and B is -CH2-, -〇-, -S-, -C0-, -S〇2_, -C(CH3)2&quot ;·,or. More preferably, the tetravalent organic groups are each independently

In a specific embodiment, the tetravalent organic group G and 11 1341851 are not particularly limited as long as the divalent organic group p contained in the proline oligomer of the formula (1) of the present invention is used. The divalent organic group P is an aromatic group, preferably a &

Rex rabbit η each Q is independent of wind (four), Cl, C4 alkyl or CrC4 perfluoride, and A is 〇_, each, -CO-, -CH2-, -〇C(〇)- or -CONH- . Better, 兮) The price of the organic group P is independent of each other.

O'

The above divalent organic group BJ P ' may also be a (iv) aromatic group, for example:

X

X -CH2 -ii- Γο-lil·-ch2- L Η1 where X is as defined above; and you and the land 'the 2-valent organic group P is the Z-order unit H 3C~EC H ih> s 1 An integer of 3, preferably c 3 c ς Η 3 i-Ο

Η 3(/ 'CJ -C Η 12 .(5 1341851 (DMSO) Depending on the product, the composition of the present invention further comprises a non-transitory ice of a polarity. ^ The aprotic solvent is selected from the group consisting of: N _Methyl to = monomethyl acetamide (DMAC), dimethylformamide (dmf), dimethyl | ^ toluene, dimethyl benzene, and combinations thereof. Including, but not limited to, additives known to those skilled in the art for use in polyimine: splicing couplers, photoinitiators, etc.

The photoinitiator suitable for use in the present invention may be, but not limited to, selected from the group consisting of dibenzophenone, diethanolone, 2-hydroxy-2-methyl-propanone, 2 , 厶dimethoxy-1,2-diphenylethan-1-one, 1·transylcyclohexyl phenyl ketone, 2,4,6-trimethyl decyl diphenylphosphine oxide, and The combination is commonly used in the following groups: 3_aminopropyltrimethoxydecane 〇\PryMOS), 3-triaminopropyltriethoxydecane (APrTE〇s), 孓Aminopyryldimethoxydecane (APTMOS), 3-aminophenyltriethoxydecane (APTE〇s), and combinations thereof. The inventors have discovered that, prior to prior art techniques for preparing polyimine The precursor composition of the present invention has a smaller molecular weight and a reduced acid group, so that it is less hygroscopic, and is more stable even if it is hygroscopic, so it can be stored at room temperature for use without storage at a low temperature ( For example: minus 20. The precursor composition of the present invention can be prepared by methods well known in the art. For example, but not by way of limitation, the formula (丨) in the precursor composition of the present invention. Dimer acid may be raised by such a manner that having the formula H2N-P-NH2 diamine and the dianhydride having the formula (4), the reaction is obtained by mixing 13 1341851 »t; square ο

,l J 111 Ν /

2 G is as defined in the text. Preferably, the amount of diamine required is calculated according to the molecular = size of the desired proline copolymer (ie, determining the m value), and the metered diamine/valid is formed into a solution in a polar aprotic solvent. Further, an appropriate amount of dianhydride is added to carry out a reaction to obtain a proline conjugate of the formula (1). By way of example (but; f is limited thereto), the diamine can be dissolved in a polar, non-f-sub-solvent selected from the group consisting of N-methyl β-ratio (ΝΜΡ), dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl ketone, (^MSO), oxime, xylene, and combinations thereof. Here, the molar ratio of the diamine to the diacid needle is in the range of 1:0.8 to 1:1.2, preferably 1:0.9 to 1:1.1. The reaction of the diamine with the dianhydride is usually carried out at a temperature of from Torr to 100 ° C, preferably from 0 to 50 Torr, usually for from 5 to 12 hours. The dish is further divided into the above steps for preparing the proline oligopolymer of the formula (1), and the aromatic dianhydride is generally used as the dianhydride of the formula (4), and examples thereof include, but are not limited to, pyromellitic dianhydride ( PMDA), 4,4-diphthalic acid dianhydride (BPDA), 4,4-hexafluoroisopropylidene dicarboxylic acid: anhydride (6FDA), 1-(trifluoromethyl)_2, 3,5,6 _ benzene tetracarboxylic dianhydride (P3FDA), 1,4-bis (tris: base)-2,3,5,6- stupid tetracarboxylic dianhydride (P6FDA), Bu dioxin base)_13 , 3_ triterpene indane-5,6-dicarboxylic dianhydride, 1-(3,4,-dicarboxyphenyl)-1,3,3-tridecyl 'feet-6,7- Dicarboxylic acid dianhydride, bis(7),-dicarboxyphenyl)_3_methylindan_5,6-di- & bis, H3VV·dicarboxy-phenyl)-3-methyl----6 7-Dicarboxylic dianhydride, 2,3,9,1〇-dinaphthyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-di-naphthalene- l,4,〗, 8_tetraacid, 2,7-dichloronaphthalene-1,4,5,8-tetra-resorcinic two-needle, 2,3,6,7-tetra-naphthalene-2,4, 5,8-tetra-rebel dianhydride, phenanthrene-1,8,9,1〇tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetradecanoic acid dianhydride, 1,2 ',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, 3,3',4,4'-dimercapto ketone tetracarboxylic dianhydride, 2,2',3,3,-biphenyltetracarboxylic dianhydride, 4,4,_isopropylidene Decanoic acid dianhydride, 3,3,·isopropylidene dicarboxylic acid dianhydride, 4,4,-oxydiglutaric acid dihydrazide M1851 = stone fluorenyl dicarboxylic acid dianhydride, 3,3'-oxygen Dibasic phthalic acid dianhydride, 4,4,-arylene diphenyl sulfonium sulphate, 4'4' thiodiphthalic acid dianhydride, 4,4'-ethylene dicarboxylic acid dianhydride, 2 ,3,6,7· 酸酸二轩, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, benzene_,,,4·4 Carboxylic dianhydride, pyridine-2,3,5,6-tetracarboxylic dianhydride, and combinations thereof. Preferably, an aromatic dianhydride selected from the group consisting of: stupid tetracarboxylic acid II = MDA), 4,4-diphthalic acid dianhydride (BPDA), 4,4-hexafluoroisopropylidene Capric acid II \ DA) 1-(difluoroindolyl)-2,3,5,6·benzenetetrahydro acid dip (P3FDA), 1,4-bis(trimethyl)-2,3,5 , 6-stupic tetracarboxylic dianhydride (P6FDA), and combinations thereof. In one embodiment, stupid tetracarboxylic dianhydride (PMDA) is employed. The aromatic diamines well known in the art can be employed as diamines of the formula t^P-NH2 (where p is as defined above) in the above process. For example (but not limited thereto), a diamine selected from the group consisting of 4,4·-diaminodiisopropyl ether (〇da), p-phenylenediamine (pPDj), and m-didecyl can be used. p-Diaminobiphenyl (DMDB), m-bis(trifluoromethyl)-p-diamine-biphenyl (TFMB), 3,3'-dimercapto-4,4,-diaminobiphenyl (〇TLD) ), 4,4,-octafluorobenzidine (OFB), tetrafluoro-p-stupidine (TFPD), ^'-tetrahydrobenzidine^(3)), 3,3'-di-diphenylaniline (DCB) ), 2,2,-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 4,4,-oxy-bis[3- (Trifluoromethane), 3,5-diaminobenzotrifluoride, tetrafluorophenylene diamine, tetrafluorophenylene diamine, tetrafluoro-phenylene Amine, i,4-bis(4.aminophenoxy)-2-t-butylbenzene (BATB), 2,2,-dimethyl-4,4,-bis(4.aminophenoxyl) Biphenyl (DBAPB), 2,2-bis[4-(4-aminophenyloxy)phenyl]hexa-propane (BAppH), 2,2·-bis[4-(4-aminobenzene) Oxy)phenyl]norbornane (BAPN), 5-amino-(4,-aminophenyl)-1,3,3-trimethyl-free, 6-aminoaminophenyl)- l,3,3-trimethylindan 4,4·-methylenebis(o-aniline), 3,3,-dichlorodiphenylamine, 3,3,_continudyldiphenylamine, 4,4'-diaminobenzophenone , i,5-diaminonaphthalene, bis(4-aminophenyl)diethyldecane, bis(4-aminophenyl)diphenylnonane, bis(4-aminophenyl)ethylphosphine Oxide, N-(bis(4-aminophenyl))-N-methylamine, N-(bis(4-aminophenyl))-N-phenylamine, 4,4 fluorene Bis(2-methyl phenylamine), 4,4'-fluorenylene bis(2-decyloxyaniline), 5,5'. methylene bis(2-aminophenol), 4,4·- Methylene bis(2-methylaniline), 4,4,-oxybis(2-decyloxy 1341851*, aniline), 4,4,-oxybis(2-aniline), 2,2 , · bis (4-amino phenol), 5,5,-oxy bis (2-amino phenyl), 4,4,-thiobis(2-mercaptoaniline), 4,4,-sulfur Bis(2-nonyloxylamine), thiobis(2-sterolamine;), 4,4'-dimethyl bis(2-methyl phenylamine), 4,4,- Bis.-(2-Ethoxyaniline), 4,4'-sulfonylbis(2-amphetamine), 5,5,-sulfonylbis(2-amidophenone), 3,3 '-Dimethyl-4,diaminobenzophenone, 3,3,-dimethoxy-4,diamine The first brewing of 1,3,3-one gas monoaminodiphenyl sulfonium, 4,4'-diamino phenyl, strepto-diamine, 4,4'-methylenediphenylamine (MDA), 4 , 4'-thiodiphenylamine, 4,4'-thinyldiphenylamine, 4,4'-isopropylidenediphenylamine, 3,3'didimethoxybenzidine, 3,3'-di Carboxybenzidine, 2,4-tolyldiamine, 2,5-nonylphenyldiamine, 2,6-methylphenyldiamine, m-diphenylphosphamide, 2,4-diamino- 5-gastric, 2,4-diamino-6-gas, and combinations thereof. Preferably, 4,4'-diaminodiphenyl ether (〇DA), p-diphenylamine (pPDA), m-dimethyl-p-diamine-based (DMDB), m-bis(trifluoromethane) P-diamino-phenyl (TBMB), 3,3'-dimercapto-4,4'-diamine-based (〇TLD), 4,4,-decylenediphenylamine (MDA), Or a combination thereof. Among them, in one embodiment, 4,4'-diaminodiphenyl ether (〇da) is used.

The compound of the formula (2) of the precursor composition of the present invention can be provided by reacting a dianhydride of the formula with a compound having a hydroxyl group in the following manner:

(2) and ίΐϋί as defined above. Preferably, 'the first is to dissolve the two _ in a polar non-mass, and then add a secret compound, the shape should be two = side has a heterogeneous (_C_R) and secret (_C_ shame compound. = not limited to this) 'The first two can be dissolved in the polarity selected from the group below. ϋ Ν Ν Ν 曱 曱 曱 曱 , , , , , 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 DMA DMA DMA DMA DMA DMA DMA The amount of the quinone σ in this ' 16 1341851 hydroxy compound is in the range of the molar ratio " · · This reaction is generally (4) to & The reaction is usually carried out for a period of time to 3 〇 = a compound having a hydroxyl group which can be used in the present invention, a glycol or a polyol, preferably a unit alcohol. It can be used for too mono-alcohol, special limitation, and can be a chain The trans, aryl chain, and alcohol are not limited thereto. The unit alcohol may be exemplified by a ruthenium to a Hi group (but an alcohol. For example: a linear or branched alkyl group of up to 14 rabbit atoms) . XH3

or

HO

/~' [η :々'ch3 CH, CH3 where ' n is the total siltation of l to 10. Private + „ branched alkyl alcohols include (for example, not limited to 旷5 core, linear chain of 1 to 14 carbon atoms or 1 λ of λ) methyl alcohol, ethyl alcohol, n-propyl alcohol, and its 舻lf group Propyl alcohol, 2-methylpropyl alcohol isopropyl, methyl butyl alcohol, methyl alcohol, neobutyl alcohol, alcohol, thiol hexyl alcohol, heptyl alcohol, and Compounds of octyl gamma in this method of financing may also be stupid, such as

'phenol, or with a photosensitive group, the photosensitive group may be an ethylenically unsaturated group, preferably having the following formula (6 & 1341851

(b) - a compound of the following formula (2)

OR OH (2); wherein R, G, Gi, P and m are as defined above, and the molar ratio of component (a) to component (b) in the composition is 0.8: 1 to 1.2 : 1, preferably 0.9: 1 to 1.1: In the case where it is not limited by theory, the present invention can be obtained by the method shown in the following φ flowchart:

19 1341851 Η21 ΑΎ; ό ο ο 〇儿 1'0>=〇 G1 ΟΛ YO ο ρ

Λν G + 2 Ν 4- ρ OAOYOG1 ΟΛ γο 〇 ο=< νπο ο

ρ ΛΎ GOAr Ν

ΟΜ Μο

In the synthesis method of the poly-imine, it is necessary to synthesize a large molecular weight poly-araminic acid as a precursor, but because the molecular weight is too high, the viscosity is too large, so that the workability is only poor, and it is easy to be leveled when coated. Disadvantages such as bad sex. In addition, when a high molecular weight polymer is formed, when the amine acid is bumped, the m-side of the time is easy; and the bond of the bond length is extremely large, causing a great internal stress, causing the coated substrate film to warp and deform. In addition, the curing temperature involved in the conventional method usually needs to be as high as 3 (8) to 35 〇t. On the other hand, the 'solid content of the poly-imide synthesis' is only about 1〇〇/0 to 30% when it is polymerized to form poly-proline, so the volume shrinkage ratio after cyclization is large. , 20 1341851 and the coating can reach the thickness required by the product and increase the difficulty of the process. Furthermore, it is known that the precursor of polyimine is highly viscous in the final dehydration and cyclization, and the solvent and water are not easily volatilized during soft baking, so that bubbles are easily generated at the time of hard baking. In contrast, the polyimine of the present invention is polymerized with a phthalic acid oligomer of the formula (2) using a phthalic acid oligomer, which is characterized in that the dianhydride derivative of the formula (2) has an ester group' (_c) (〇)〇R) and, the base group of (-C(O)OH), is in a metastable state (meta staWe are still lean), so it does not have a diamine-proline at room temperature. The oligomer produces a reaction, and since the proline oligo has a low molecular weight, the handleability is good, and the coating can achieve a leveling effect. At the time of post cure, when the temperature rises above 100, the proline oligomer will start to produce intramolecular cyclization, and the diamine at the end of the proline oligomer can also simultaneously (<: (0_ lysine (_C(0)0H) terminal group, reduced to acid liver, further reaction polymerization into larger molecules, and then condensation to provide a combination of excellent thermal, mechanical and tensile properties Yttrium imine. Compared with the prior art, due to the use of polyglycine containing a phthalic acid oligomer (small viscosity) as a precursor, a small viscosity, rather than a high viscosity polymer, When coating, it can exhibit high leveling property and workability. In addition, since the composition of the composition of the present invention has a small molecule, the interaction between the polymer and the molecular chain can be avoided when performing the imide. The high internal stress caused by the shortening of the bond length, and the contained proline oligomers are first undergone intramolecular cyclization, and Φ undergoes intermolecular polymerization and cyclization, thereby effectively reducing polyimine Remaining! ^ stress, has the advantage of not warping. In addition, the composition of the present invention can be relatively low The curing reaction is carried out at a temperature (about 250. (: to 300 Å, which further reduces the operating cost. The polyimine of the present invention, due to its precursor composition having a high solid content, is about 25 Between % and 50%, it can reduce the consumption of solvent, shorten the soft baking time and reduce the soft baking temperature, and has the advantages of fast film forming speed and reducing the number of coatings required to reach the required thickness of the product. Generally, molecular polymerization will add some monomer or short-chain polymer, so that the knife and the molecule can form a cross-link (cr〇ssUnking). When the precursor composition of the present invention has a photo-polymerizable a group, and because the molecule is small, it can be cured

Claims (1)

'Patent scope: A precursor composition for providing a polyimine, which comprises (a) a proline oligomer having the following formula (1) (1); and (b) a compound of the following formula (2) R is each independently a linear or branched alkyl group having from 14 carbon atoms, a phenol group or a ethylenically unsaturated group; G and G! may be the same or different and each independently is a tetravalent organic group; P is a divalent organic group; and m is an integer from 1 to 1; and wherein the molar ratio of component (a) to component (b) is from 0.8:1 to 丨.2:j. The composition of claim 1, wherein the ethylenically unsaturated group is selected from the group consisting of: ίΪ: allyl, ethylphenyl, propyl phenyl, propyleneoxymethyl, ketone, Propyloxypropyl, propyloxybutyl, propyloxy, propyloxyhexyl, methacryloxymethyl, methacryloxyethyl, 1341851 methacryloxypropyl, Mercapto butyloxybutyl, decyl propylene oxypentyl, methacryloxyhexyl, a group having the following formula (7), and a group having the following formula (3) R2 〇 -〇-R J- (3) H2C=c- WJ, where Ri is a C2-C "chain", a straight chain or a branched chain, a CrQ ring, a linear chain, a linear chain or a branch a chain and R2 is a hydrogen or a CrC4 alkyl group. A straight or branched chain CrC8 is extended to an alkyl group; 3. A composition according to claim ,, wherein R Μ ο is H2C=C~C—0—C2H4— π H2C= c~-c~~〇^C2li4 H2〇=C- I i? -o-ch2-ch-ch2 OH CH3O H2C= C—c— O— ch2- ch—ch2— OH o 1341851 «CH·, CH3 -ch3, -ch2ch3, -ch2ch2ch3, ch3, h2c-ch3, ch3 or CH3 4. The composition of claim 1, wherein the tetravalent organic group is selected from the group consisting of: Wherein each Y is independently hydrogen, halogen, Crc4 alkyl, or CrC4 perfluoroalkyl; and B is -CH, ·-Ο-, -S-, -CO-, -S〇2·, -C(CH3 ) 2_, or -C(CF; j)2-. 5. The composition of claim 4, wherein the tetravalent organic group is selected from the group consisting of: 6. The composition of claim 1 wherein the divalent organic group is selected from the group consisting of: 3 1341851 鏖j » Φ wherein X is independently hydrogen, haloalkyl, or crc4 perfluoroalkyl; A is -〇-, -s-, -CO-, -CHr, -0C(0)-, or -CONH-; And z are each an integer of 1 to 3. 7. The composition of claim 6 wherein the divalent organic group is selected from the group consisting of: Ch2— and 8. The composition of claim 1, wherein m is an integer from 5 to 50. 9. The composition of claim 1, wherein the molar ratio of component (a) to component (b) is from 0.9:1 to 1.1 Μ. 10. The composition of claim 1 further comprising a polar aprotic solvent selected from the group consisting of N-mercaptopyrrolidone (NMP), dimethylacetamide 1 MAC), dimercapto Indoleamine (DMF), dimercaptopurine (DMSO), methyl stupid, dimethyl strepone, and combinations thereof. U. The composition of claim 1, further comprising a coupling agent selected from the group consisting of: 3-aminopropyltrimethoxy fluorene (APrTM®), 3·triamine Propyltriethoxydecane (APrTEOS), 3-aminophenyltrimethoxysilane (APTMOS), and 3-aminophenyltriethoxydecane (apte®), and combinations thereof. /,, ' 12. The composition of claim 1, further comprising a photoinitiator selected from the group consisting of dibenzophenone, benzophenone, and 2-hydroxyl_2曱基_丨_笨丙嗣, 2D dimethoxy-1,2-diphenylethan-1-one, 1-yl-cyclohexyl-phenyl-, 2,4,6-trimethyl Alum-based diphenylphosphine oxide, and combinations thereof. 13. A polyimine which is polymerized using a composition of the following components: (a) - a proline condensate having the following formula (1) σ m ο); a compound of the following formula (2) OH OR 1341851 A ^ 11 *· OR OH (2); wherein the molar ratio of component (8) to component (b) is from 0.8:1 to 1.2:1; and R, G, Gi, P and m are as claimed 1 definition. 14. The polyimine of claim 13, wherein the ratio of the molar number of the component (a) to the molar ratio of the component (b) is from 0.9:1 to U:1.