JPS58179230A - Partial hydrolysis of poly(iminoimidazolidindione) - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a new copolymer and a method for making the same.

The preparation of poly(parabanic acid) has been widely developed. Poly(paraban #R), also named poly(1,3-izomezolidine-2,4,5-trione), can be prepared by acid hydrolysis of iminoimidazolidinedione and repeatedly Contains an imidazolidine di/ring in the unit.

1 O-C-C20 Poly(iminoimidazolidinedione) and Poly(Rose)
Methods for the preparation of both 2-cup and 7-ton noodles are well known and are described in co-assigned U.S. Pat. No. 661.859.
Poly(/serapanic acid) can also be produced by other methods such as those described in US Pat. No. 3,609,113.

Poly(iminoimidazolidinedione) can be synthesized by the reaction of hydrogen cyanide with one or more polar diincyanates, the reaction of dicyanopolamide with one or more polar diincyanates, or the combination of cyanoformamidylisocyanate, and has a repeating unit. It contains a 1,3-imidazolidinedione-1,3-diyl ring having the following structure. However, NH in the formula is at the 4 or 5 position.

U.S. Pat. No. 3,661,859 discloses that the degree of hydrolysis can be controlled by the amount of acid used, particularly depending on the molar concentration of imino groups to be hydrolyzed for complete hydrolysis. It is taught that corresponding molar amounts of acid are required.

In common wI! Inventor's U.S. Patent No. 4,028 issued
No. J11 states that when using sulfuric acid for hydrolyzing poly(iminoimidazolidinedione), high temperature, e.g.
It is disclosed that stoichiometric amounts of sulfuric acid can only be used between 110° C. and 110° C., since at lower temperatures the ammonium hydrogen sulfate formed is slowly and incompletely converted to ammonium sulfate and km. , +1. Ammonium hydrogen sulfate was insufficient to induce the desired hydrolysis of 75T. Therefore, sufficient acid reaction was prevented at low temperatures. However, at high temperatures, sulfuric acid Mizukiba rapidly converted to ammonium sulfate and sulfuric acid. The advantage of using sulfuric acid in a chemical system with a maximum temperature of only 45° C. was that a product containing some non-hydrolyzable groups could be produced. That is, the degree of hydrolysis was not marketable under such conditions.

parabanic acid/iminoimidazolidinedione copolymer, i.e. iminoimidazolidinedione-1,3-di-
It has now been discovered that copolymers containing both diyl and imidazolidinetrione-1,3-diyl rings in a particular range of proportions have particular desirable properties which are heretofore unknown.

Some elm parabanic acid polymers have been found to have a low glass transition temperature, so magnetic tape (requiring good dimensional stability in microscopic tape), μ'' printed circuits, Films used in Kelpur packaging materials, fibers such as tire cord fibers (requires tensile strength and elastic modulus), molded products for electrical connectors, bearings, magnetic wire insulation materials, cables, cooking utensils, glass fibers. It is particularly suitable as a coating for industrial belts (requiring high temperature resistance). Generally these polymers are highly thermally degradable. However, parabanic acid polymers are susceptible to attack by certain solvents, and in many applications these polymers cannot be used alone and must be thermally crosslinked to increase their solvent resistance. .

Although poly(iminoimidazolidinedione) polymers, poly(parabanic acid) polymer precursors, have very poor solvent resistance, these polymers crosslink more easily and usually attack parabanic acid polymers. It was found that the material was insoluble in the demolition process.

A preferred embodiment of the invention is a repeating unit Ikuji Q-) (→“ In the cross-polluted copolymer with fMI repetition.

The structural formula of the unit Q or 6 to 25 is O 1, (), - 1
Imidazolidinedione-1,3-diyl ring (circle P
A) and about 75 to 97% of the structural formulas are 1-N''+-6-1-.

is an imidazolidinedione ring (PPA), where R in the repeating [2 units is an organic moiety which is aliphatic, cycloaliphatic, aromatic or a mixture thereof, and n represents the solid product & ! It is a copolymer that is large enough to be constructed.

Another aspect of the invention is a crosslinked product of the nine polymers defined above. Heating the polymer at 200 to 300°C for 10S to 24 hours will result in crosslinking.Does the crosslinked product need to be solvent resistant or impermeable, such as winding of the polymer? Desirable and useful.

When the polymer is prepared according to the procedure of U.S. Pat. No. 5,661,859, R is the organic moiety of the diisocyanate. (7) Diisocyanates can be selected from a wide group having a wide range of organic moieties.
Oxo, ester, alkylthio, arylthio, nitro groups, etc. do not react with incyanate groups, so buy a new one. Functional groups with active hydrogen atoms (eg, carboxylic acids, phenols, amines, etc.) should not be present.

The particular diisocyanate used is described in U.S. Pat.
No. 661,859, other % pestles, literature or organic teachings known to those skilled in the art - IF K are shown. Preferred R groups include methylene diphenyl, mexidiphenyl, a mixture of methylene diphenyl and 4-methyl-1,3-7]nynylenyl, and methylene diphenyl/l/J-k:,') I
There is a mixture of J-rangeyl.

Poly(iminoimidazolidinedione) polymer (PIP
A) 'i partially hydrolyzed KPIPA in the polymer
and PPAtJt from 3 to 25- and 7, respectively.
It has been found that by preparing copolymers containing 5 to 97, thermally stable and easily crosslinking polymers are produced. The crosslinked L7 product has side bath agent properties.

That is, they are insoluble in solvents that normally dissolve PIPA or PPA polymers.

The Yen/A polymer is also crosslinked and becomes solvent resistant, but the partially hydrolyzed PIPA/P patented in this specification
)・Requires harsher heat treatment than A copolymer.

The partially hydrolyzed polymers of the present invention also exhibit excellent adhesion to other materials such as metals.

The ease of crosslinking is directly related to the increase in PIPA units in the copolymer chain, but the hydrolyzed units (1-'l
-・A, 1st place) Q) At the same time as F decreases, the polymer becomes small in heat 1'', and polymers with a PPA index unit of 75 or less are undesirable due to the small sluggishness of 1. History P
Polymers with an IPA of about 3 or less do not exhibit improved properties and are qualitatively identical to fully hydrolyzed PPA polymers with respect to crosslinking and adhesion to metals.

Another aspect of the invention is imidazolidinedione-1,3-
This method uses sulfuric acid to hydrolyze the diyl ring.

In the embodiment -, the present invention provides the following structural units (wherein one X is O and the other X is N
A method for producing a copolymer containing a repeating rate (wherein X of the -force is 0, the other X is NH, and R in the repeating unit is an aliphatic, an organic moiety which is of the formula Jll!IA, aromatic or a mixture thereof;
iminoimidazolidinedione-1 in the polymer, with the presence of water hydrolyzing the NH groups; n is sufficiently large to yield a solid polymer;
The 6-diyl ring is contacted with as little as the molar amount corresponding to the ring (preferably less than 99 cs of the molar amount of said ring) of -basic Prensted acid, and a substantially stoichiometric amount, relative to the aK present, of Iminoimidazolidinedione in polymers
The initial temperature of the reaction mixture is preferably room temperature (i.e., about 20-25°C) to allow the reaction to proceed for a time sufficient to convert the 1,3-diyl ring to the imitazolidinetrione ring. ).

Thus, the amount of monobasic acid used is more or less sufficient to convert all of the iminoimidazolidinedione-1,3-diyl rings of PIPA, and preferably the amount of monobasic acid used is less than or equal to converting all of the iminoimidazolidinedione-1,3-diyl rings of PIPA. Applications of degraded copolymers are described by Tad El Baton.
"J, of Organic Ch @
amino hydrides (amtnohy
aration) which forms a new class of molecular materials for use as such or as intermediates in the preparation of other polymers (by reaction of the aino groups by conventional procedures known to those skilled in the art). .

The conversion of PIF to PPA requires 1 mole of hydrogen ions per mole of tsindasilidinedione ring (or repeating unit). Thus, substantially stoichiometric conversions can be obtained by controlling the molar ratio of acid to iminoimidazolidinedione rings.

A multi-X polymer precursor characterized by a 1,3-imidazolidinedione ring is contacted with water of a Bronsted acid such as hydrochloric acid, chlorobromic acid, sulfuric acid, formic acid, etc. or anhydrous hydrogen chloride or hydrogen bromide. By doing so, the water layer reaction can be carried out. When the polymer comes into contact with water or is precipitated in water, hydrolytic decomposition of the imino groups occurs, yielding a highly hydrolyzed polymer containing both PIP and PPA.

The P-PA precursor polymer prepared by any of the methods described earlier in the technology may be precipitated from the reaction solvent during the synthesis at the ninth stage of reaction selection. After the combination has occurred, the inocyanate and the precursor polymer (which may be precipitated in a reactive or non-reactive mixture) are then solidified.
PIP is hydrolyzed either as a solid suspension or dissolved in a suitable solution.

111! Oral degradation may be carried out to the desired degree of turbidity. However, when the solid PIPA precursor material is contacted with an appropriate molar ratio of anhydrous hydrogen chloride,
Partial hydrolysis may be caused by contacting the water with water.

The bath solution of PIB-based polymer (PIB) can also be partially hydrolyzed using a machine for those who have synthesized PIPA by any of the known methods as mentioned above. It may be because it is an electric bath. The d-liquid may be formed by dissolving the 9MU animal-based polymer in a preferred bath medium.

It has been found that partial hydrolysis causes some degree of deterioration of the polymer (reduction in intrinsic viscosity).

This deterioration is particularly noticeable in the case of sulfuric acid in some cases. Preferably, an aqueous solution of a monobasic acid is used for the partial hydrolysis. - #Ii basic acids are used at lower temperatures than sulfuric acid to carry out partial hydrolysis.
The degradation of the polymer that occurs during partial hydrolysis is in sharp contrast to complete hydrolysis, where the intrinsic viscosity of the PPA polymer product is virtually identical to that of the PIPA precursor member.

Although J4 technology has also been developed using sulfuric acid for partial calohydrolysis to minimize degradation, -basic acid power is preferred. - Preferred procedures using basic rIR initiate partial hydrolysis at all (approx.
This is a method in which il: is approximately 45°C. Similarly, a template can be used conveniently, but since the water volume of IWi is readily available, 1 mole of sulfuric acid can be added to about 5 moles of imino in P-P during the first 15 minutes of hydrolysis. There will be a water layer of 〃1''. However, the VLC version of hydrolysis! S continues to increase as ammonium hydrogen deoxygenate is converted to chain acid, and the conversion rate (home country % IfF No. 4.02fi611
/JIJ) will depend on the temperature and time of the water splitting reaction.

80 to 110°C, preferably not exceeding 90°C, for a short period of time, for example, 10 minutes or less, with an electric key not exceeding 6 moles of water per 1 mole of imino group, preferably not more than 2 moles of water per 1 mole of imino group. It was found that using yM m of sulfuric acid in the presence or absence, the low F intrinsic viscosity of the polymer was split and was within the acceptable range. For the purposes of this paper, a polymer with a decrease in intrinsic viscosity of 6 Ls or less is acceptable for producing a useful product. However, - in the case of basic acids, no particular consideration is given to these limits, and the deterioration is hardly detected; - in the case of basic acids, upon hydrolysis. According to the stoichiometry, there should be at least 1 mole of water per mole of imino group, and in reality there should be at least 2 moles of water.

In general, PIPmu and ppmu are soluble in dipolar aprotic solvents with moderate hydrogen bonding. Suitable solvents include dimethylformide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide and N-methylpyrrolidone. These may be used in mixtures with each other or with oily aprotic solvents such as benzene, toluene, xylem, methyl acetate, ethyl acetate, anisole, phenetol, butyl benzoate, chlorobenzene, etc.

For purposes of illustration, examples illustrating the invention are set forth with respect to specific polymers. That is, Exxon Research and Engineering Department (Ixxon)
Res@aroh'and lngin@ering
Oom) any) from diphenylmethane diisocyanate according to the technology of the patentee described in the patent issued! ia! at! The polyiminoimidazolidinedione is a polyiminoimidazolidinedione having a yr<-rtm return unit.

However, in the formula, the force X is 0, and the other X is NH
The product of complete hydrolysis of this precursor is a localized polymer having repeating units t''M of the structure shown below.

This also has 7 paris (1,4-phenylenemethylene-
1,4-phenylene-1,,5-(izedazolidine-2
, 4, 5-)] and 4, chemical abstract
ts) K is polyC (2,4,5-trioxo-1,3
-1,4-phenylene methylene/-1,4-phenylene]. The glass rolling temperature of this product is 275°C or higher, and it cannot be extruded or made into metal.

Convenience, on these poly! -m respectively
and PI'muM, diphenylmethane 1 is placed in other organic moieties 1! It is introduced that the partially hydrolyzed product (P-P-P-P) can be cleaved from other polyiminoimidazolidinediones (PxP) as shown in Figure 7. It will be.

In addition to polymers, softeners, antioxidants, UV stabilizers, S
Poly such as fuel, pigment, photoresist, etc. It is conceivable that suitable machining of the seaweed without impairing the scales may also be present in the compositions of the present invention.

West - Intrinsic viscosity is determined by using dimethylformua as the # line,
KLL5F poly! in 100m solution! − held a memorial service#
9. Measured at 25°C at 1 degree.

1 This example describes the hydrolysis of PIP-M with a small amount of hydrochloric acid and demonstrates the influence of the undesirable JIJ water screen on the thermal crosslinkability of the product. When less acid than chemical filtering was used for the hydrolysis of M, iminoimida l lysine dione moieties and imitazolidine trione (Noripan 11111) jlt were contained in the reversible unit.

1601 (JQI 5 CIIQ64 %kl) PI
PA-M repeat 41. A bath solution containing units was used. The solvent was dimethylformamide (DM?). 160j
l') Measured d (') 37.9 glutinous hydrochloric acid was added to the solution while stirring. After 45 minutes, the polymer was precipitated by mixing with water in the chamber. The amount of acid used, the η work of the imino groups hydrolyzed by the acid, the intrinsic viscosity of the polymer, and the dissolution of the powdered product in dimethylformamide aged 20 (24 h in JYQ) in total air. All products, whose properties are shown below, were soluble in dimethylformand before aging.

B 1109 10&4 1
06 Kua (Ll()4
1DL5 H14 submersible D 11
087 85.0 104 Insoluble 1 [105856-6 (197 Insoluble F
[10121t7 104 insoluble (al MPA-M repeating unit (11024mopB
Number of moles of HDI in b.

(a) 24alr&! at 200℃ The dimensions of the soluble and insoluble gel of the polymer powder in dimethylform 1 at room temperature after aging are D (imitation powder gel).
From Ii,? (very coarse, large gel). All polymers were mu I# before heating.

2 This example describes the hydrolysis of PIP-M using a sufficient amount of acid to completely convert PIP-M to PP-M.

PIPA-M (vinh-101) 192.5p (
To 1 oa 2 p of a dimethylform 1 zedo solution containing the repeating unit (L6957), add 37 eulysalt ell 5a4F (H
A solution of od 11592% A, ), 27 p of water, and 200 d f) of dimethylformamide was added. The solution was stirred without heating for 30'' minutes. Then 1 ton of bath
-F to remove precipitated ammonium chloride. The polymer was precipitated by mixing Solution F with water. The dry product is 185t, and the ultimate viscosity is U98, which is 6. A weak band (0-M) at 5.98μ of the A band) and a strong band at 5.74μ unique to the carbonyl group in 1 mitazolidinetrione ring were observed.

Nitrogen? r; 6i11 constant 1't! 1181; calculated value 1α82 m (resistance based on the expected 85.2-hydrolysis of imino groups in pxpmu-M);
L extended. After drying in a vacuum oven at 12 Llu, the film was soluble in dimethylformamide. However, after aging at 260° C. for 1 hour, the film became insoluble in the solvent. h aged under the same conditions
A film of 1 is soluble in dimethylform 1 and t(
.

"1~) PIPA-M (yinh=LO1)19 1 liter of dimethylformamide containing 1 Sp (repeat unit a698 mol)
lil 10867, 57 excellent tllelt 64.
81 (MCI (1657%), water 3i, L2F
, & dimethylformamide 2QOxd (Qllfll
Added t#i. +Peng had 20i hits and 1W1411.

The convergence of the polymer is 190p, and the intrinsic viscosity is [198
Met. JR spectrum includes iminoimidazolyle/
Absorption peaks specific to both dione and imida l-lysine trio/ring were observed; electrical conductivity analysis: #I constant value ILL28 excellent;
Calculated value 1α37tII (the imino group in PmuM is a
94.1-Hydrolyzed as expected.

A film of this polymer with a thickness of 5 x 10-'am (2 mils) was cast from dimethylformamide and the dried film was soluble in dimethylformamide at 260°C.
After aging for 1 hour, it remains soluble even after 6 hours. 260℃
It became insoluble in the sacrificial solvent aged for 2 hours. For comparison, I investigated the film of PP-M, which was also destroyed, and found that even after being converted to 2Q at 260C.
It was a bath.

n −-4 pxph-*0rnh-101) 1891 (repeat unit α682 mol) kl methylformamide bath solution 1
061, 37' AjMtl & 66.619 (MC
I (1672%), water 64.6p, and dimethylborumamide 2OL1. The first fluid of Z/ was squeezed out. −
3J shellfish was similar to Hei2.

, J': The yield of Lima - is +80P and 'hshi, the limit N
K! It was d to 1. -Water analysis; measured value IQ
121ti value 11114 excellent (ttJl assuming that the imino group in PLF A-M is hydrolyzed to 9a5's as predicted theoretically).

Column 5 This example V uses PIP-M using acid from the foothills where there are many storms necessary for complete conversion to PIPA-Mt-PPA-M.
Describe the hydrolysis of

PIPA-M(ylnh-?, 01) 2 Qt
37% 4# 75.5p in 11134F solution containing 8p (0729 moles of M return units)
A solution of (HOf 1765%), water 61P and trimethylformamide 2'00d was added. The procedure was the same as for Hei 2. The yield of polymer is 200p
#, ri @ viscosity is LOll” 6, +, m elemental analysis: #
J constant 11[1[1131i PPA-M related calculations [1[107fi.

-2, 6, 4 and 5 polymer particles extend ft.
- Compare the crosslinking properties of the film and its adhesion to steel foil. Copper foil is rolled annealed (roll@dann@al)
It was a treated 2a35p (1 oz.) steel foil.

Based on pictures 2.6.4 and 5, the solution of the molecular product is
65 wJ of dimethylformand K for 1 op of each polymer.
11ll! To do this, a steel foil strip (2,54C1lX 15.2411+11 (1 inch x 6 inches)) was prepared and coated with a steel foil. It was dry recorded at 150C.

Each coated copper wire is 4JJIIfr. Even if a crease is made, the film will not cut or separate from the steel foil. When the steel foil to be coated was immersed in dimethylformamide, all of the film was dissolved, so none of the films were crosslinked.

Memorized nine steel foil aged at 260℃ for 1 hour 7
L and others remain firmly attached to the T-be-C copper foil, and the tl
There was no breakage or cracking at r l) eyes t') tl.

- When immersed in dimethylformamide, films of polymers threaded with f15.4 and 5 disintegrate and bleed, whereas films of polymer made with f15. I couldn't layer it.

Film coatings of the polymers loaded on 1fN2 and 3 aged for 214 hours at 260°C were insoluble in dimethylformamide and only adhered to the rope even on specimens immersed in the solvent for 48 hours. Two other film coverings M (made of polymers described in n4 and 5)
The steel was resistant to dimethylformamide, but when immersed in the solvent, it separated from the steel and floated to the surface. These results indicate that there is a difference in the transferability of the film to copper. This difference is likely due to the presence of the iminoimidazolidinedione ring in the polymer, and is clearly due to the presence of the iminoimidazolidinedione ring in the polymer. The roughness of such rings in the Schiff/polymer is as described in 7.
I #sex rdandai-Truvc was low. The foregoing results also indicate that the crosslinking rate is in a linear convergence of 1s degrees of the iminoimidazolidinedione rings in the polymer.

Example 7 650p (2.64 moles of repeating units) of PmuM (η1nh-t
07) was heated to 60°C with stirring.6
Next was 4i & result of 9&3rd attack 107.3jl (t 05
mol) was added, immediately followed by the addition of a solution of 253P in water in dimethylformamide.

Temperature f: raised to 85°C. After 15 minutes, add reaction #1 solution to 6
0UK cooled and insoluble ammonium sulfate t-
It was removed and precipitated in water. The intrinsic viscosity of the product is α58
Met. i1 elemental analysis: measured value 1a43 arrogant; calculated value 1u
skl (1 ftK for the 4-predicted 89.71 hydrolysis of the imino groups in PIPA-M).

Example 8 688 p (2.48 mol m return units) of PIPA-M (+21 nh-
107) was heated to 60°C. then 96
．． 12 p (118 mol) of sulfuric acid 12 was added, followed immediately by a solution of 26 ab9J) water in 26a5jl of dimethylformamide. 85℃
The product was heated for 150 minutes and the product was knitted using the same procedure as fC Ryohei 7. The product Q) was 165.

d JC>su4me ": σ4rint+ml t13
1% 1iTtJEfl & 1 [132% (calculated assuming that 95,1 dominant force water splits).

Conocopolymer and PPmuM film (thickness 5XI
C1og(zmil)) was treated with tAt from a methylformamide bath. After aging for 1 day at 240 °C, the following mechanical properties show that the elongation of the heat-treated laminate is reduced and the tensile strength at break is lower than 1. .PPA-M film is this)
The outside electricity does not change and the skin.

PPA-M: i4 excellent 15,200pθ' 2
7'14,400P" female 'film:'・
14 14,950 16 14.6
50? -ri'S Seven Nights-74 Hours Aging PPh-u: 13 16,950 32
15.900 row B film'
It should be noted that even if a partially hydrolyzed polymer having an intrinsic viscosity lower than 111a200PP is produced by sulfuric acid, the tensile strength is improved.

Example 9 PIPmu-M of 7219 (2.60 mol unit) in 3240 p of dimethylformamide (da1nh=[L
99) containing solution IfLft heated to 60°C 1 then 9
&6 129.9 p (L276 mol) of sulfuric acid was added, followed immediately by sidelining of a solution of 281 p of water in 281 p of dimethylformamide. After heating to 85° C. for 15 minutes, the p-polymer was isolated using the same procedure as in month 7. The intrinsic viscosity of the polymer was [83].

¥Ill tree analysis: Measured Mfli11 [114%; Calculated value I
CL 16% (ItJl assuming that the imino group in Pxph-M is pre-hydrolyzed with 9al, which is predicted by J4 ceramics)
.

A film of this copolymer and P-type PA-M (thickness 5×
10-'m (2 mil)) and then drained from the dimethylformade solution. The mechanical properties shown below are based on the temperature of the film at 240°C for one day. 111. The concentration of imino groups in the copolymer film was clearly superior to that of V in distinguishing it from PP-M, indicating that it is not.

PPA-M 14% 15,200Ps127
% 14,400 pli Film of Example 9 14
15,300 49 15.4002
After aging for 24 hours at 40°C PP mu-u 13 16.950 32
1 to 900 row 9 film 1614,300
15 14.650 examples 10 P engineering Pmu-M (yinh=(L99) 2001
(ILK return unit [L722 mol)] Add 36.5% salt to 1215p of dimethylformia I#l solution containing 56% salt.
9p (Hod 1 i4731 i CL3694) was added, and then a solution of 781 water in 220p dimethylformamide was added. The temperature increased from 23°C to 36°C due to the heat generated by the reaction. After stirring for 30 minutes, the solution was filtered and precipitated. Ammonium chloride was removed from 7 and Fa was mixed with water to precipitate siborimer. Polymer li@viscous is [L98, IIS Analysis: Measurement 111i 12
．． 545G; Calculated value: 12.56 (assuming that the imino group in PA-M was subjected to 511 pre-hydrolysis, which is predicted by the method! 1K).

The polymer readily dissolves in dimethylformamide, but when heated at 260° C. for 60 minutes, no ftvk remains.

Nishi-2 (Winh-C) 16t5p (repeating unit α586 mol) in 820p dimethylformamide
The 67.5-salt 11153.2jl (HO
A bath solution containing I 19.959 ; α 546 mol) was added. The maximum reaction temperature was 65°C. Pass the liquid through for 60 minutes to remove precipitated ammonium chloride. Shibolimer was precipitated by mixing P solution with water. The intrinsic viscosity of the polymer is 103, which is 9. Iil analysis: Measured value 1a38ch; Calculated value 1u39 (Imino 1 in P-P-M is hydrolyzed as 9-gun 1 as predicted by salt theory. calculation).

Example 12 280 p of K PD'A-M (
Daron 1, tJ6) 5b, 4jl (mi Shihan Q (12
0 mol) 2 m solution containing 1" was heated to 60°C. Next, 9.167 (IJ, 90 mol) of 9&3-sulfuric acid was cooled, and immediately a solution of 36P water and 729 dimethylformamide was poured into the mixture. While stirring the solution,
From 95℃! IO Minuteki U was feverish. It was then cooled and passed through P. The transparent product was mixed with water to precipitate the product, which had an intrinsic viscosity of LL44.

Based on the acid formula used for hydrolysis, the imino groups in PIFA-M should have been hydrolyzed by 90 units.

Raw, 1 piece film from gold dimethylformamide 6I
I received C treatment. After aging at 260° C. for 5 hours, it became insoluble in dimethylformamide, but was cast in the same way. P
The PA-M film was similarly exposed to heat when exposed to heat.

Example 1 Compare the results of 14 reactions in which 95 of the imino groups in PA-M are hydrolyzed with sulfuric acid. The concentration of water in the reaction static solution and the reaction time were varied. A common fist is PIFA-
The Mm solution was heated to 60°C, and then sulfuric acid and water were added. Addition of 771 JL of sulfuric acid (α95 moles of hydrogen ions) to 11 moles of imino in solution.

The amount of water added to the plants was very rare among woodcutter. S* from 85 to 88℃
at various times (10, 20, or 30
) Heat the reaction solution quickly in an ice-water bath. Next, use water to poly! - was precipitated. The intrinsic viscosity of the polymer was measured.

The reaction values of the products produced by all reactions were identical to each other and to the product prepared in Example 8 (95,1 pre-hydrolyzed).

The concentrations of reactants, reaction times, and intrinsic viscosity of the molecular products are summarized below.

The intrinsic viscosity of the product varies from L67 to t03 with respect to the intrinsic viscosity of the original PIPA-M. Since the intrinsic viscosity of PPA-M sauce (manufactured by hydrolyzing the imino group by 1 ounce) is substantially the same as that of the starting material PIPA-M, the viscosity of 1 or less in the above experiment was P.I.P.A.
It shows that the molecular weight decreased during the partial hydrolysis of -M.

It was unrelated to the amount of sulfuric acid in the bath (DMFI Ay).

The reduction in molecular weight was accelerated when the reaction time was long (compare the intrinsic viscosities of the products of experiments C and M and D and N).

The drop in water increases as the water content increases. 6 hours, 20 minutes and 50 minutes reaction, e.g.
F, G, H, I and J each other and to each other, I,, M
and N44'' are particularly clear when compared with each other. 10
In the 1 minute reaction, one drop of water had little effect on polymer degradation.

This drop in molecular weight that occurs during the reactions described at 1 tariff, 8.9 and 12-C was unexpected since %J 1 to 5 O-C was not shot.

The difference between the two experiments lies in the acid used for hydrolysis. When using hydrochloric acid, heating is not necessary; when using ii acid, hydrogen ion/hydrogen ions of both acids are used for hydrolysis, as described in U.S. Pat. No. 4.02a311. The @kai needs Toguchi fever.

III, o o Zuo Example 14 MPmuM (η1n
h-134) 171 (m return unit cL0614)
64jl (10162 mol) of sulfuric acid t64jl (10162 mol) of 9 & 9 to convert 52.8 molar mass-top PIPA rings into a solution containing
Added 0 next! A solution of 9p water in 51LI of dimethylformazide was added. The solution was not heated. α5°2.6.24 and 72 hours later, polyi-i was precipitated by mixing with liquid gold water, and the intrinsic viscosity of each polymer was measured. The results below show that the intrinsic viscosity of the polymer in solution is gradually decreasing.

Experiment reaction time (hours) η1nhm
α5 t21B
2 t220
6 t14D 2
4 1051it 72
1185 each product thin (thickness approx. 2.54
X10-'3(α11l)) film was gold cast and an IR spectrum was obtained. The intensity of the 1670ts-' (onj! specific) tlC&- absorption peak decreased slowly compared to other absorption peaks. This indicates that θ-oral decomposition continues for the last 70 hours, although at a very slow rate, or that the imino group disappears due to decomposition of the iminoimino/lysine dione ring to some extent. r, in the latter case the intrinsic viscosity of the ti polymer decreases. IX reaction on both sides is happening. This A
rather substantial degradation (Example 1 for 45 minutes using HOJ)
(compare with the experiment of
This is the result of completely incomplete use of sulfuric acid at temperatures as low as ℃.

Patent agent and patent attorney Yukizo Yamazaki 1- +A Anshi 1-I J:1
111 large and small Showa 1. , /'(I(1, "I ii'l hope('!
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Claims (1)

[Scope of Claims] (1) In a crosslinkable copolymer having a repeating unit ÷ Q-1 (→ t), the repeating unit q has a structural formula of about 3 to 25 (wherein one X is O is Toshi, the other χ is N
and an imidazolidine trio/III having a structural formula of about 75 to 97, and R in the 7 repeating units is aliphatic or alicyclic. , aromatic or a mixture thereof, and n is sufficiently large to yield a solid composition. (2. Crosslinkable cobo IJ according to claim 1)
A copolymer characterized in that in y-, the R group is methylene diphenyl. (31) The stable meltable composition according to claim 1, characterized in that the R group is oxydiphenyl. (4) The stable meltable composition according to claim 1 in which the R group is methylene diphenyl and 4-methyl-1
, 3-phenylenyl groups. (5) A copolymer in the stable meltable composition according to claim 1, in which the R group is a mixture of methylene diphenyl and hylylene diyl groups. (6) Repeating unit (I1), in the formula, X of the force is O, the other X is Nil, R in the 7 repeating units is aliphatic,
a polymer having an organic moiety that is cycloaliphatic, aromatic or a mixture thereof, and n is large enough to form a solid product) with a monobasic Brønsted acid ( However, in the method of producing a copolymer having one unit of XtiO in the formula and the other X of NI, @+J tfx2 Hk at about 20 to 25°C in the presence of water.
In the first M leakage, 9996 ms less than the number of moles of the inoimitazolidinedione-1,5-diyl ring in the polymer is used, and substantially chemical w1 is used for the acid present.
A method in which the reaction is allowed to proceed without cooling for a sufficient period of time to convert the pre-gd iminoi epsilon dasylidine dione-1,3-diyl ring in 1 it of the polymer to an imidazolidine trione ring. (7) In the method according to claim 6, #I
- A method in which the basic acid is selected from hydrochloric acid or hydrobromic acid. (8) %flf In the method according to claim 7,
@Note - A method characterized in that the basic acid is hydrochloric acid. (9) The method according to claim 8, wherein the method uses an aqueous acid solution to reduce mold. (II % 1-Restation range) In the method according to any one of Items 6, 7, or 8, 1 to 1 to 1 to 1,6-diyl rings present in the iminoimidazolidinedione-1,6-diyl ring present in the polymer. 11. A method according to claim 10, wherein 99 molar capsules of said acid are present. A method in which the presence of 97 mol of the above-mentioned - is defined as % mold. (121 repeating 1.7 units (12, where one X is 0, R in the repeating unit is aliphatic, alicyclic,
(where n is large enough to yield a solid product) comprising contacting the polymer with a sparge (with the proviso that only one part of the aromatic compound is aromatic or a mixture thereof) The force X is 0 and pl the other X i
iN)] in which the iminoimidazolidinedione-1, iminoimidazolidinedione-1,
About 0.5 to 495 moles of the acid based on the 5-diyl ring are added at a temperature of 80 to 110°C with up to 6 moles of water per mole of iminoimidazolidinedione-1,5-diyl ring. using a sufficient time to convert the iminoimidazolidinedione-1,6-diyl ring of the tS wrinkle to an imidazolidinetrione ring,
How to make it a sign. (131) [The method according to claim 12, characterized in that the temperature of the cliff is 90°C or lower. imidazolidinedione-1,5-diyl ring 1
A process characterized in that less than 2 moles of water are present per mole. (151% Claim No. 12, No. 13 or No. 14)
A process according to any of the preceding paragraphs, characterized in that the reaction time is such that the intrinsic viscosity of the product copolymer does not fall below 94% that of the starting polymer.